Functionalized nanoparticles

ABSTRACT

The present invention discloses functionalized nanoparticles comprising on the surface a covalently bound radical of the formula (I) wherein the nanoparticles are SiO 2 , Al 2 O 3  or mixed SiO 2  and Al 2 O 3  nanoparticles, and wherein the general symbols are as defined in claim  1 . These functionalized nanoparticles are for example useful as stabilizers and/or compatibilizers in organic materials, or as photoinitiators in pre-polymeric or pre-crosslinking formulations, or as reinforcer of coatings and improver of scratch resistance in coating compositions for surfaces.

The present invention relates to novel functionalized nanoparticles, tocompositions comprising an organic material, preferably a syntheticpolymer, and to the novel functionalized nanoparticles, as well as tothe use thereof as stabilizers and/or flame-retarders and/orcompatibilizers for organic materials which are subject to oxidative,thermal or light-induced degradation, in particular syntheticnanocomposite polymers or coatings; or as photoinitiators for thein-situ polymerization or hardening of pre-polymeric nanocomposites tonanocomposite materials.

The use of fillers in polymers has the advantage that it is possible tobring about improvement in, for example, the mechanical properties,especially the density, hardness, rigidity or impact strength of thepolymer.

Using extremely small filler particles (<400 nm), so-called nano-scaledfillers, mechanical properties, long term stability or flame retardantproperty of the polymers can be improved at a much lower concentrationof 5 to 10% by weight compared to 20 to 50% by weight with themicro-scaled normal filler particles. Polymers containing nano-scaledfillers show improved surface qualities like gloss, lower tool wear atprocessing and better conditions for recycling. Coatings and filmscomprising nano-scaled fillers show improved stability, flameresistance, gas barrier properties and scratch resistance.

Nano-scaled fillers possess an extremely large surface with high surfaceenergy. The reduction of the surface energy and the compatibilization ofthe nano-scaled fillers with a polymeric substrate is therefore evenmore important than with a common micro-scaled filler in order to avoidaggregation and to reach an excellent dispersion of the nano-scaledfiller in the polymer. The nano-scaled fillers like the phyllosilicatesare made organophilic by ion exchange, for example with alkylammoniumsalts. Such nano-scaled organophilic phyllosilicates are betterswellable and easier to disperse (exfoliate) into a polymer matrix [forexample Nanomer® from Nanocor or Closite® from Southern Clay Products].

WO-A-03/002652 discloses the preparation of additive functionalizedorganophilic nano-scaled fillers.

It has now been found that a selected group of novel functionalizednanoparticles are especially useful as stabilizers and/orflame-retarders and/or compatibilizers for organic materials which aresubject to oxidative, thermal or light-induced degradation, inparticular synthetic nanocomposite polymers or coatings; or asphotoinitiators for the in-situ polymerization or hardening ofpre-polymeric nanocomposites to nanocomposite materials.

This invention therefore relates to a functionalized nanoparticlecomprising on the surface a covalently bound radical of the formula I

whereinthe nanoparticle is a SiO₂, Al₂O₃ or mixed SiO₂ and Al₂O₃ nanoparticle,X is oxygen, sulfur or

R₁ is C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

hydroxyl-substituted C₂-C₂₄alkyl which is interrupted by oxygen, sulfuror

C₂-C₂₄alkenyl, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, a polymerizablegroup, a polymer, or an additive selected from the group consisting ofradical scavengers, hydroperoxide decomposers, UV-absorbers, lightstabilizers, flame retardants and photoinitiators;R₂ and R₃ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl, C₇-C₉phenylalkyl, —OR₅,

R₄ is hydrogen, C₁-C₂₅alkyl or C₃-C₂₅alkyl which is interrupted byoxygen or sulfur;R₅ is hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygenor sulfur; C₂-C₂₄alkenyl, phenyl, C₇-C₉phenylalkyl,

or the nanoparticle surface,R₆ and R₇ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl, C₇-C₉-phenylalkyl or —OR₅,R₈, R₉ and R₁₀ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl or C₇-C₉phenylalkyl, and n is 1, 2, 3, 4, 5, 6, 7 or 8.

Highly preferred nanoparticles comprising a radical of formula (I) arethose of formula

wherein R₁, R₂, R₃, X and n are as defined under formula (I) and whereinR₅ as nanoparticle surface is —SiO₂ surface.

Of interest is also a functionalized nanoparticle comprising on thesurface a radical of the formula I and comprising on the surfaceadditionally a covalently bound radical of the formula II

whereinthe nanoparticle is a SiO₂, Al₂O₃ or mixed SiO₂ and Al₂O₃ nanoparticle,R₁₁ is C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

amino-, mercapto- or hydroxyl substituted C₂-C₂₄alkyl; amino-, mercapto-or hydroxyl substituted C₂-C₂₄alkyl which is interrupted by oxygen,sulfur or

C₂-C₂₄alkenyl, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, a polymerizablegroup or a polymer,R₁₂ and R₁₃ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl, C₇-C₉phenylalkyl, —OR₁₅,

R₁₄ is hydrogen, C₁-C₂₅alkyl or C₃-C₂₅alkyl which is interrupted byoxygen or sulfur;R₁₅ is hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygenor sulfur; C₂-C₂₄alkenyl, phenyl, C₇-C₉phenylalkyl,

or the nanoparticle surface,R₁₆ and R₁₇ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl, C₇-C₉phenylalkyl or —OR₁₅,R₁₈, R₁₉ and R₂₀ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl or C₇-C₉phenylalkyl.

Highly preferred nanoparticles comprising a radical of formula (II) arethose of formula

wherein R₁₁, R₁₂ and R₁₃ are as defined under formula (II) and whereinR₁₅ as nanoparticle surface is —SiO₂ surface.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,icosyl or docosyl.

Hydroxyl-substituted C₂-C₂₄alkyl is a branched or unbranched radicalwhich contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups,such as, for example, hydroxyethyl, 3-hydro-oxypropyl, 2-hydroxypropyl,4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl,4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl,5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl,7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl,3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl,6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl,2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 1′-hydroxyundecyl,12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl,15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl,18-hydroxyoctadecyl, 20-hydroxyeicosyl or 22-hydroxydocosyl. A preferreddefinition of R₂₂, R₂₃, R₂₄ and R₂₅ is hydroxyl-substituted C₂-C₁₂alkyl,especially hydroxyl-substituted C₄-C₈alkyl.

C₃-C₂₅Alkyl which is interrupted by oxygen, sulfur,

for example, CH₃—O—CH₂CH₂—, CH₃—NH—CH₂CH₂—, CH₃—NH(CH₃)—CH₂CH₂—,CH₃—S—CH₂CH₂—, CH₃—O—CH₂CH₂—O—CH₂CH₂—, CH₃—O—CH₂CH₂—O—CH₂CH₂—,CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂—,CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—O(CO)—CH₂CH₂— orCH₃CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—O(CO)—CH₂CH₂—.

Hydroxyl-substituted C₂-C₂₄alkyl which is interrupted by oxygen, sulfuror

for example, —CH₂—CH(OH)—CH₂—O—CH₃, —CH₂—CH(OH)—CH₂—O—CH₂CH₃,—CH₂—CH(OH)—CH₂—O—CH(CH₃)₂ or—CH₂CH₂—CO—O—CH₂CH₂—O—CO—(CH₂)₅—O—CO—(CH₂)₅—OH.

Amino-, mercapto- or hydroxyl substituted C₂-C₂₄alkyl is, for example,—CH₂—CH(NH₂)—CH₂—O—CH₃, —CH₂—CH(SH)—CH₂—O—CH₂CH₃ or—CH₂—CH(OH)—CH₂—O—CH(CH₃)₂.

Amino-, mercapto- or hydroxyl substituted C₂-C₂₄alkyl which isinterrupted by oxygen, sulfur or

for example, HO—CH₂CH₂—O—CH₂CH₂—, H₂NCH₂CH₂—NH—CH₂CH₂—,HOCH₂CH₂—NH(CH₃)—CH₂CH₂—, HOCH₂CH₂—S—CH₂CH₂—,H₂NCH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—, HOCH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—,HSCH₂CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—,H₂NCH₂CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂—H₂NCH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—,HSCH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—O(CO)—CH₂CH₂— orHOCH₂CH₂CH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂—O(CO)—CH₂CH₂—.

Alkenyl having 2 to 24 carbon atoms is a branched or unbranched radicalsuch as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference isgiven to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6,especially 3 to 4 carbon atoms.

C₅-C₁₂cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.Preference is given to cyclohexyl.

C₅-C₁₂cycloalkenyl is, for example, cyclopentenyl, cyclohexenyl,cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenylor cyclododecenyl. Preference is given to cyclo-hexenyl.

A polymerizable group is, for example,

A polymer is the polymerization product when a polymerizable group, asfor example outlined above, is polymerized.

C₇-C₉Phenylalkyl is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenyl-ethyl. Preference is given to benzyl.

Examples of photoinitiators, from which the residue R₁ may be derived,are the following: camphor quinone; benzophenone, benzophenonederivatives, such as 2,4,6-trimethylbenzophenone, 2-methyl benzophenone,3-methyl benzophenone, 4-methylbenzophenone, 2-methoxycarbonylbenzophenone 4,4′-bis(chloromethyl)benzo-phenone, 4-chlorobenzophenone,4-phenylbenzophenone, 3,3′-dimethyl-4-methoxy-benzophenone,[4-(4-methylphenylthio)phenyl]-phenylmethanone,methyl-2-benzoylbenzoate, 3-methyl-4′-phenylbenzophenone,2,4,6-trimethyl-4′-phenylbenzophenone,4,4′-bis(dimethylamino)benzophenone,4,4′-bis(diethyl-amino)benzophenone; ketal compounds, as for examplebenzildimethylketal (IRGACURE® 651);

acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenyl ketones or 2-hydroxy-2-methyl-1-phenyl-propanone (DAROCUR® 1173),1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE® 184)1-(4-dodecylbenzoyl)-1-hydroxy-1-methyl-ethane,1-(4-isopropylbenzoyl)-1-hydroxy-1-methyl-ethane,1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one(IRGACURE®82959);2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one(IRGACURE® 127);2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-propan-1-one;dialkoxyacetophenones, α-hydroxy- or α-aminoacetophenones, e.g.(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane (IRGACURE® 907),(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (IRGACURE® 369),(4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane(IRGACURE® 379),(4-(2-hydroxyethyl)aminobenzoyl)-1-benzyl-1-dimethylaminopropane),(3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane;4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, e.g.dimethyl benzil ketal, phenylglyoxalic esters and derivatives thereof,e.g. oxo-phenyl-acetic acid 2-(2-hydroxy-ethoxy)-ethyl ester, dimericphenylglyoxalic esters, e.g. oxo-phenyl-acetic acid1-methyl-2-[2-(2-oxo-2-phenyl-acetoxy)-propoxy]-ethyl ester (IRGACURE®754);oxime esters, e.g. 1,2-octanedione1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (IRGACURE® OXE01), ethanone1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)9H-thioxanthene-2-carboxaldehyde 9-oxo-2-(O-acetyloxime), peresters,e.g. benzophenone tetracarboxylic peresters as described for example inEP 126541, monoacyl phosphine oxides, e.g.(2,4,6-trimethylbenzoyl)diphenylphosphine oxide(DAROCUR® TPO),bisacylphosphine oxides, e.g.bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE® 819),bis(2,4,6-trimethyl benzoyl)-2,4-dipentoxyphenylphosphine oxide,trisacylphosphine oxides,halomethyltriazines, e.g.2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-methyl-4,6-bis-trichloromethyl-[1,3,5]triazine, hexaarylbisimidazoles,e.g. ortho-chlorohexaphenyl-bisimidazole,ferrocenium compounds, or titanocenes, e.g.bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrryl-phenyl)titanium(IRGACURE®784).

Examples of flame retardants, from which the residue R₁ may be derived,are the following

Representative organohalogen flame-retardants are for example:

Polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.),decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate (PB 370®, FMC Corp.),tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl)phosphate,chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid,bis-(N,N′-hydroxyethyl)tetrachlorphenylene diamine, poly-β-chloroethyltriphosphonate mixture, tetrabromobisphenol A bis(2,3-dibromopropylether) (PE68), brominated epoxy resin,ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),bis(hexachlorocyclopentadieno)-cyclooctane (DECLORANE PLUS®),chlorinated paraffins, octabromodiphenyl ether,hexachlorocyclopentadiene derivatives, 1,2-bis(tribromophenoxy)ethane(FF680),

tetrabromo-bisphenol A (SAYTEX® RB100), ethylenebis-(dibromo-norbornanedicarboximide) (SAYTEX® BN-451),bis-(hexachlorocycloentadeno) cyclooctane, PTFE,tris-(2,3-dibromopropyl)-isocyanurate, andethylene-bis-tetrabromophthalimide.

Suitable phosphorus containing flame-retardants are for example:

Tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel),tetrakis(hydroxy-methyl)phosphonium sulphide, triphenyl phosphate,diethyl-N,N-bis(2-hydroxyethyl)-amino-methyl phosphonate, hydroxyalkylesters of phosphorus acids, ammonium polyphosphate (APP) or (HOSTAFLAM®AP750), resorcinol diphosphate oligomer (RDP), phosphazeneflame-retardants, ethylenediamine diphosphate (EDAP), phosphonates andtheir metal salts and phosphinates and their metal salts.

Nitrogen containing flame-retardants such as isocyanurateflame-retardants include polyiso-cyanurate, esters of isocyanuric acidand isocyanurates. For example, an hydroxyalkyl iso-cyanurate such astris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate,tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl isocyanurate.

Nitrogen containing flame-retardants include melamine basedflame-retardants, examples of which are:

Melamine cyanurate, melamine borate, melamine phosphates, melaminepolyphosphate, melamine pyrophosphate, melamine ammonium polyphosphateand melamine ammonium pyrophosphate.

Nitrogen-containing flame-retardants comprise compounds of formulae IIIto VIIIa

whereinR⁴ to R⁶ are each independently of the others hydrogen, C₁-C₈alkyl,C₅-C₆cycloalkyl or C₁-C₄alkyl-C₅-C₆cycloalkyl, each unsubstituted orsubstituted by hydroxy or C₁-C₄-hydroxyalkyl; C₂-C₈alkenyl,C₁-C₈-alkoxy, -acyl, -acyloxy, C₆-C₁₂aryl, —O—R² or —N(R²)R³, and R² andR³ are hydrogen, C₁-C₄alkyl, C₅-C₆cycloalkyl, C₂-C₈alkenyl,C₁-C₄hydroxyalkyl or C₆-C₁₂aryl, with the proviso that R⁴ to R⁶ are notsimultaneously hydrogen and also, in formula II, not simultaneously—NH₂, and in formula VII at least one group is present which is capableof adding a proton;R⁷ to R¹¹, each independently of the other, have the same possiblemeanings as R⁴ to R⁶ with the exception of —N(R²)R³, X is the anion of aproton donating acid, x is the number of protons transferred from thelatter to the triazine compound and y is the number of protonsabstracted from the proton donating acid;or represent ammonium polyphosphate, a melamine ammonium phosphate, amelamine ammonium polyphosphate, melamine ammonium pyrophosphate, acondensation product of melamine or/and a reaction product of melaminewith phosphoric acid or/and a reaction product of a condensation productof melamine with phosphoric acid or mixtures thereof.

Examples are benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin,glycoluril, melamine cyanurate, melamine phosphate, dimelaminephosphate, melamine pyrophosphate, urea cyanurate, melaminepolyphosphate, melamine borate, ammonium polyphosphate, melamineammonium polyphosphate or melamine ammonium pyrophosphate, preferably acondensation product of melamine from the series melem, melam, melonand/or a higher condensed compound or a reaction product of melaminewith phosphoric acid and/or a reaction product of condensation productsof melamine with phosphoric acid or a mixture thereof. Special emphasisshould be given to: dimelamine pyrophosphate, melamine polyphosphate,melem polyphosphate, melam polyphosphate, and/or a mixed polysalt ofsuch a type, more especially melamine polyphosphate.

Halogenated flame-retardants may be selected from organic aromatichalogenated compounds such as halogenated benzenes, biphenyls, phenols,ethers or esters thereof, bisphenols, diphenyloxides, aromaticcarboxylic acids or polyacids, anhydrides, amides or imides thereof;organic cycloaliphatic or polycycloaliphatic halogenated compounds; andorganic aliphatic halogenated compounds such as halogenated paraffins,oligo- or polymers, alkylphosphates or alkylisocyanurates. Thesecomponents are largely known in the art, see e.g. U.S. Pat. Nos.4,579,906 (e.g. col. 3, lines 30-41), 5,393,812; see also PlasticsAdditives Handbook, Ed. by H. Zweifel, 5^(th) Ed., Hanser Publ., Munich2001, pp. 681-698. Halogen contained in these compounds usually ischloro and/or bromo; preferred are brominated flame-retardants for suchsystems.

Phosphorus containing flame-retardant may be selected from phosphazeneflame-retardants, which are well known in the art. They are disclosedfor example in EP1104766, JP07292233, DE19828541, DE1988536, JP11263885,U.S. Pat. Nos. 4,107,108, 4,108,805 and 4,079,035 and 6,265,599.

The phosphorus containing flame-retardant may be selected from metal ormetalloid salts of a phosphonic acid of formula X

wherein R is hydrogen, C₁-C₁₈alkyl, C₅-C₆cycloalkyl, C₂-C₆alkenyl,C₆-C₁₀aryl or C₇-C₁₁aralkyl and R′ is hydrogen, C₁-C₈alkyl, C₆-C₁₀arylor C₇-C₁₁aralkyl, the substituents R and R′ that are other than hydrogenbeing unsubstituted or substituted by halogen, hydroxyl, amino,C₁-C₄alkylamino, di-C₁-C₄alkylamino, C₁-C₄alkoxy, carboxy orC₂-C₅alkoxycarbonyl; and the metal or metalloid is from Group IA, IB,IIA, IIB, IIIA, IVA, VA or VIII of the Periodic Table. The salts may bepresent as simple ionic compounds comprising anions of phosphonic acidand cations of the metal or metalloid. When R′ is hydrogen and the metalor metalloid has a valency of more than one, the salt can have apolymeric structure according to the following formula XI

wherein R is as defined hereinbefore, M is a metal or metalloid, n has avalue corresponding to the valency of M minus 1, m is a number from 2 to100 and wherein each group

is bonded only to M atoms.

The phosphonic acid salts according to the definition either are knownor can be prepared in accordance with methods known per se. Examples ofsuch methods are to be found in, inter alia, EP-A-245 207, pages 4 and 5to 7 (Examples 1 to 14).

PTFE, polytetrafluoroethylene (for example Teflon® 6C; E. I. Du Pont),may also be mentioned, as disclosed in WO 03/016388.

Of interest are functionalized nanoparticles comprising on the surfaceat least a radical of the formula I and optionally a radical of theformula II, wherein

R₁ is an additive selected from the group consisting of phenolicantioxidants, benzofuran-2-ones, sterically hindered amines, aminicantioxidants, 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, phosphites,phosphonites, thioethers, benzophenones, α-activated acetophenones,bisacylphosphinoxides (BAPO), monoacylphosphinoxides (MAPO),alkoxamines, thioxanthones, benzoins, benzil ketals, benzoin ethers,α-hydroxy-alkylphenones and α-aminoalkylphenones.

Of special interest are functionalized nanoparticles comprising on thesurface at least a radical of the formula I and optionally a radical ofthe formula II, wherein

R₁ is

R₂₄ is C₁-C₂₅alkyl, hydroxyl-substituted C₂-C₂₄alkyl;hydroxyl-substituted C₂-C₂₄alkyl which is interrupted by oxygen, sulfuror

C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₂₅ is C₁-C₂₅alkyl or C₂-C₂₅alkenyl,R₂₆ is hydrogen or methyl,R₂₇ is hydrogen or methyl,R₂₈ is hydrogen or

R₂₉ is C₁-C₄alkylene,R₃₀ and R₃₁ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₇-C₉phenylalkyl, phenyl or C₅-C₈cycloalkyl,R₃₂ and R₃₃ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₇-C₉phenylalkyl, phenyl or C₅-C₈cycloalkyl,R₃₄ and R₃₅ are each independently of the other hydrogen, halogen,C₁-C₄alkyl, —CN, trifluoromethyl or C₁-C₄alkoxy,R₃₆ is a direct bond or —O—,R₃₇ is hydrogen, —O^(), C₁-C₂₅alkyl, C₂-C₂₀alkenyl, C₂-C₂₀alkinyl,C₁-C₂₀alkoxy, C₅-C₁₂cycloalkoxy, C₇-C₂₅aralkoxy, C₆-C₁₂aryloxy,C₇-C₉phenylalkyl, C₅-C₁₂cycloalkyl, phenyl, naphthyl, hydroxyethyl,C₂-C₂₅alkanoyl, benzoyl, naphthoyl or C₂-C₂₀alkoxyalkanoyl,R₃₈ is hydrogen or an organic radical, R₃₉ and R₄₀ are eachindependently of the other hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl orphenyl,R₄₁ is hydrogen, halogen or C₁-C₁₈alkyl,R₄₂ is hydrogen, C₁-C₁₈alkyl or C₇-C₉phenylalkyl,R₄₃ and R₄₄ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈alkoxy,di(C₁-C₄alkyl)amino, hydroxyl or

R₄₅ is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkoxy or

R₄₆ and R₄₇ are each independently of the other hydrogen, hydroxyl,C₁-C₁₈alkyl, phenyl,C₁-C₁₈alkoxy or C₇-C₉phenylakyl,R₄₈ is a direct bond or oxygen,R₄₉ and R₅₀ are each independently of the other C₁-C₁₈alkyl,C₇-C₉phenylalkyl, cyclohexyl, phenyl, or phenyl substituted by 1 to 3alkyl radicals having in total 1 to 18 carbon atoms,R₅₁, R₅₂ and R₅₃ are each independently of the others hydrogen, halogenC₁-C₄alkyl or C₁-C₄alkoxy,R₅₄ is C₁-C₂₀alkyl, C₅-C₈cycloalkyl, C₇-C₉phenylalkyl or phenyl,R₅₅ is C₁-C₂₅alkyl,R₅₆ is methylene or ethylene,R₅₇ is methylene or ethylene,R₆₂ is hydrogen or C₁-C₁₈alkyl,R₆₃ and R₆₄ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈alkoxy, C₁-C₄alkylthio, morpholinyl, C₇-C₉phenylalkyl of phenyl,R₆₅ and R₆₆ are each independently of the other C₁-C₁₈alkyl, isC₂-C₄alkylene,R₆₈ is hydrogen or C₁-C₁₈alkyl,R₆₉ is C₃-C₇alkylene,R₇₀ and R₇, are each independently of the other C₁-C₈alkyl orC₇-C₉phenylalkyl,R₇₂ and R₇₃ are each independently of the other C₁-C₈alkyl or R₇₂ andR₇₃ are together —CH₂CH₂—O—CH₂CH₂— thus forming with the nitrogen atomto which they are attached a morpholinyl ring,R₇₄ is hydrogen, C₁-C₁₈alkyl or C₇-C₉phenylalkyl, andx is 1, 2 or 3.

Of very special interest are functionalized nanoparticles comprising onthe surface at least a radical of the formula I wherein n is 3.

Also of interest are functionalized nanoparticles comprising on thesurface at least a radical of the formula I wherein R₄ is hydrogen orC₁-C₄alkyl.

Of very special interest are functionalized nanoparticles comprising onthe surface at least a radical of the formula I and optionally a radicalof the formula II, wherein

R₁₁ is C₁-C₁₈alkyl, C₃-C₁₈alkyl which is interrupted by oxygen orsulfur; or 3-aminopropyl.

The functionalized nanoparticles according to the present invention havepreferably a spherical shape.

Preferably, the nanoparticles have particle size below 1000 nm,especially below 500 nm and more preferably below 400 nm. A particlesize below 300 nm, especially below 100 nm, is preferred. For example,the nanoparticles have a particle size of 10 to 1000 nm, preferably 10to 500 nm, and more preferably 40 to 500 nm. Highly preferred is aparticle size of 40 to 400 nm.

The organic content of the nanoparticles according to the presentinvention is, for example, 5 to 80 percent by weight, especially 10 to70 percent by weight, based on the total weight of the nanoparticle.

Nanoparticles are typically silicon dioxide, aluminum oxide, aheterogeneous mixture thereof or silicon aluminum oxide as mixed oxides.The silicon aluminum oxide nanoparticles according to the presentinvention can show silicon contents in between 1 to 99 metal-atom %.

It is preferred that the functionalized nanoparticle is a silica (SiO₂)or alumina (Al₂O₃) nanoparticle, especially a silica nanoparticle.

Relating to a specific application the expert would preferably useparticles showing an index of refraction close to the matrix material.Using pure silicon dioxide (n_(D) 1.48 to 1.50) or pure aluminum oxide(n_(D) 1.61) or silicon aluminum oxides with the whole range of siliconto aluminum ratio covers material with an index of refraction from 1.48to 1.61.

Unmodified nanoparticles are commercially available from differentsuppliers such as Degussa, Hanse Chemie, Nissan Chemicals, Clariant,H.C. Starck, Nanoproducts or Nyacol Nano Technologies as powder or asdispersions. Examples of commercially available silica nanoparticles areAerosil® from Degussa, Ludox® from DuPont, Snowtex® from NissanChemical, Levasil® from Bayer, or Sylysia® from Fuji Silysia Chemical.Examples of commercially available Al₂O₃ nanoparticles are Nyacol®products from Nyacol Nano Technologies Inc., or Disperal® products fromSasol. The artisan is aware of different well-established processes toaccess particles in different sizes, with different physical propertiesand with different compositions such as flame-hydrolysis(Aerosil-Process), plasma-process, arc-process and hot-wallreactor-process for gas-phase or solid-phase reactions or ionic-exchangeprocesses and precipitation processes for solution-based reactions.Reference is made to several references describing the detailedprocesses, such as EP-A-1 236 765, U.S. Pat. No. 5,851,507, U.S. Pat.No. 6,719,821, US-A-2004-178530 or U.S. Pat. No. 2,244,325,WO-A-05/026068, EP-A-1 048 617.

The preparation of the functionalized nanoparticles comprising on thesurface at least a radical of the formula I is preferably carried out bythe reaction of corresponding nanoparticles (like unfunctionalizedsilica or alumina nanoparticles) with a compound of the formula (Ia)

whereinX is oxygen, sulfur or

R₀ is C₁-C₂₅alkyl,R₁ is hydrogen,R₂ and R₃ independently of each other are hydrogen, C₁-C₂₅alkyl,C₃-C₂₅alkyl which is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl,phenyl, C₇-C₉phenylalkyl or —OR₅,R₄ is hydrogen, C₁-C₂₅alkyl or C₃-C₂₅alkyl which is interrupted byoxygen or sulfur;R₅ is hydrogen or C₁-C₂₅alkyl, andn is 1, 2, 3, 4, 5, 6, 7 or 8.

The reaction of the compound of formula (Ia) with the nanoparticles canbe carried out in analogy to known processes. The reaction can, forexample, be carried out in an organic medium or preferably a mixture ofwater with an organic medium. As organic medium sovents like alcohols,especially methanol or ethanol can be used. It is preferred to carry outthe reaction at temperatures like 20 to 90° C., especially 40 to 60° C.As to the compounds of formula (Ia) it is preferred to use those,wherein at least one of R₀, R₂ and R₃ is methoxy or ethoxy, especiallywherein R₀, R₂ and R₃ are methoxy or ethoxy. It is highly preferred thatR₀, R₂ and R₃ are methoxy. If desired, the products obtained can beredispersed in a suitable medium, like ethanol, toluene or xylol.

In a further step the reaction product of the nanoparticles with thecompound of formula (Ia) can easily be derivatized to obtainnanoparticles comprising radicals of the formula (I) by known processessuch as for example esterification, amidation, Michael addition oropening of epoxides.

In the following some examples of such reactions are given in generalterms:

a) Nanoparticles, showing active linkage groups such as —SH or —NH₂ (forexample nanoparticles as prepared in Example 1) can easily surfacemodified with additives bearing for instance ester-, epoxy-, carboxy-,carbonyl-, acrylic-, methacrylic-, alkylhalogenide-, alkylsulfate-,anhydride-, terminal double bond-, nitrile- and for instanceα,β-unsaturated carbonyl-groups. The chemistry of these substances andthe molecular organic syntheses (like nucleophilic substitutions,nucleophilic additions, Michael additions, ring-opening reactions,radical addition, etc.) are well known and can easily be adapted to thesolid phase organic chemistry.b) Nanoparticles, showing functional groups on their surfaces, such asester-, epoxy-, carboxy-, carbonyl, acrylic-, methacrylic-,alkylhalogenide-, alkylsulfate-, anhydride-, terminal double bond-,nitrile- and for instance α,β-unsaturated carbonyl-groups can easilyfurther reacted with additives bearing —SH, —RNH (R=organic group) or—NH₂ groups with the chemical reactions mentioned above under a) [e.g.Example 23].c) Additives showing —OH, —RNH(R=organic group) or —NH₂ groups can beactivated by using acryloylchlorid under basic conditions to generateadditive-acrylates (acylation), that can easily be reacted withparticles bearing —SH or —NH₂ groups by using a Michael addition [e.g.Examples 5, 14]. Other syntheses that are leading to functional groupsmentioned in a) and b) are well known.d) Additives can be functionalized by using reactive alkoxysilanesshowing functional groups and mechanisms as mentioned in a), b) or c)and then being grafted onto the particle surface using a state of theart silanisation reaction [e.g. Example 17].

According to an alternative process for the preparation of nanoparticlescomprising radicals of formula (I) corresponding unfunctionalizednanoparticles, like commercially available silica or Al₂O₃nanoparticles, can be reacted with a compound of the formula (Ia),wherein Ro, R₂ and R₃ are as defined above under formula (Ia) and n, Xand R₁ are as defined above under formula (I). By this route thenanoparticles of formula (I) can be obtained directly, without furtherderivatization. The reaction conditions can be chosen as given above forthe reaction of the nanoparticles with the compound of formula (Ia). Thereaction can, for example, be carried out in analogy to the preparationprocess described in WO-A-03/002652.

The radical of formula (II) can be introduced in analogy to the abovepreparation processes. These reactions can be carried out simultaneouslywith the introduction of the radical of formula (I), or stepwise.

The functionalized nanoparticles of the present invention comprising onthe surface at least a radical of the formula I and optionally a radicalof the formula II are suitable for stabilizing or flame-retarding and/orcompatibilizing organic materials, which are subject to oxidative,thermal or light-induced degradation, in particular synthetic polymersor coatings, or for photoinitiating in-situ polymerization or hardeningof pre-polymeric nanocomposites or sols to nanocomposite materials.

Examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is gene-rated in-situ; propylene/butadienecopolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexenecopolymers, ethylene/alkyl acrylate copolymers, ethylene/alkylmethacrylate copolymers, ethylene/vinyl acetate copolymers orethylene/acrylic acid copolymers and their salts (ionomers) as well asterpolymers of ethylene with propylene and a diene such as hexadiene,dicyclopentadiene or ethylidene-norbornene; and mixtures of suchcopolymers with one another and with polymers mentioned in 1) above, forexample polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinylacetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

32. Pre-polymeric monomers or oligomers of the aforementioned polymersor blends.

33. Sols, especially organosols, as stable liquid suspensions ofcolloidal nano-particles in a diluent, a reactive (e.g. crosslinking)diluent or in a polymerizable or crosslinking monomer, or in a mixtureof all.

The present invention relates therefore also to a composition comprising

-   a) an organic material subject to oxidative, thermal or    light-induced degradation [component a)], and-   b) at least a functionalized nanoparticle of the present invention    comprising on the surface at least a radical of the formula I and    optionally a radical of the formula II [component b)].

Preferred organic materials are polymers, for example a pre-polymer fora nanocomposite material, in particular synthetic polymers, for examplethermoplastic polymers. Polyamides, polyurethanes and polyolefins areparticularly preferred. Examples of preferred polyolefins arepolypropylene or polyethylene.

The incorporation of the functionalized nanoparticles of the inventionand optional further components into the polymer is carried out by knownmethods such as dry blending in the form of a powder, or wet mixing inthe form of solutions, dispersions or suspensions for example in aninert solvent, water or oil. The functionalized nanoparticles of theinvention and optional further additives may be incorporated, forexample, before or after molding or also by applying the dissolved ordispersed additive or additive mixture to the polymer material, with orwithout subsequent evaporation of the solvent or thesuspension/dispersion agent. They may be added directly into theprocessing apparatus (e.g. extruders, internal mixers, etc.), e.g. as adry mixture or powder or as solution or dispersion or suspension ormelt.

The incorporation can be carried out in a heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is preferably carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the functionalized nanoparticles or additive blend tothe polymer can be carried out in all customary mixing machines in whichthe polymer is melted and mixed with the additives. Suitable machinesare known to those skilled in the art. They are predominantly mixers,kneaders and extruders.

The process is preferably carried out in an extruder by introducing theadditive during processing.

Particularly preferred processing machines are single-screw extruders,contra rotating and co rotating twin-screw extruders, planetary-gearextruders, ring extruders or co kneaders. It is also possible to useprocessing machines provided with at least one gas removal compartmentto which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffex-trusion, Vol. 1 Grundlagen, Editors F. Hensen, WKnappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, preferably 35-48screw diameters. The rotational speed of the screw is preferably 10-600rotations per minute (rpm), very particularly preferably 25-300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process can also be carriedout at a level lower than maximum throughput by varying the parametersmentioned or employing weighing machines delivering dosage amounts.

If a plurality of components is added, these can be premixed or addedindividually.

The functionalized nanoparticles of the invention and optional furtheradditives can also be sprayed onto the polymer material. They are ableto dilute other additives (for example the conventional additivesindicated below) or their melts so that they can be sprayed alsotogether with these additives onto the material. Addition by sprayingduring the deactivation of the polymerisation catalysts is particularlyadvantageous; in this case, the steam evolved may be used fordeactivation of the catalyst. In the case of spherically polymerisedpolyolefins it may, for example, be advantageous to apply thefunctionalized nanoparticles of the invention, optionally together withother additives, by spraying.

The functionalized nanoparticles of the invention and optional furtheradditives can also be added to the polymer in the form of a masterbatch(“concentrate”) which contains the components in a concentration of, forexample, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% byweight incorporated in a polymer. The polymer must not be necessarily ofidentical structure than the polymer where the additives are addedfinally. In such operations, the polymer can be used in the form ofpowder, granules, solutions, and suspensions or in the form of lattices.

Incorporation can take place prior to or during the shaping operation.The materials containing the functionalized nanoparticles of theinvention described herein preferably are used for the production ofmolded articles, for example rotomolded articles, injection moldedarticles, profiles and the like.

Of special interest are also compositions wherein the composition is acoating composition and component (a) is an organic film-forming binder.

Of special interest are transparent coating compositions which aftercuring lead to transparent coatings.

The coating composition is preferably a coating material or paint,especially an aqueous coating material or an aqueous paint.

Examples of coating materials are lacquers, paints or varnishes. Thesealways contain an organic film-forming binder in addition to other,optional components.

Preferred organic film-forming binders are epoxy resins, polyurethaneresins, amino resins, acrylic resins, acrylic copolymer resins,polyvinyl resins, phenolic resins, styrene/butadiene copolymer resins,vinyl/acrylic copolymer resins, polyester resins, UV-curable resins oralkyd resins, or a mixture of two or more of these resins, or an aqueousbasic or acidic dispersion of these resins or mixtures of these resins,or an aqueous emulsion of these resins or mixtures of these resins.

Of particular interest are organic film-forming binders for aqueouscoating compositions, such as, for example, alkyd resins; acrylicresins, two-component epoxy resins; polyurethane resins; polyesterresins, which are usually saturated; water-dilutable phenolic resins orderived dispersions; water-dilutable urea resins; resins based onvinyl/acrylic copolymers; and hybrid systems based on, for example,epoxy acrylates.

More specifically, the alkyd resins can be water-dilutable alkyd resinsystems which can be employed in air-drying form or in the form ofstoving systems, optionally in combination with water-dilutable melamineresins; the systems may also be oxidatively drying, air-drying orstoving systems which are optionally employed in combination withaqueous dispersions based on acrylic resins or copolymers thereof, withvinyl acetates, etc.

The acrylic resins can be pure acrylic resins, epoxy acrylate hybridsystems, acrylic acid or acrylic ester copolymers, combinations withvinyl resins, or copolymers with vinyl monomers such as vinyl acetate,styrene or butadiene. These systems can be air-drying systems or stovingsystems.

In combination with appropriate polyamine crosslinkers, water-dilutableepoxy resins exhibit excellent mechanical and chemical resistance. Ifliquid epoxy resins are used, the addition of organic solvents toaqueous systems can be omitted. The use of solid resins or solid-resindispersions usually necessitates the addition of small amounts ofsolvent in order to improve film formation.

Preferred epoxy resins are those based on aromatic polyols, especiallythose based on bis-phenols. The epoxy resins are employed in combinationwith crosslinkers. The latter may in particular be amino- orhydroxy-functional compounds, an acid, an acid anhydride or a Lewisacid. Examples thereof are polyamines, polyaminoamides,polysulfide-based polymers, polyphenols, boron fluorides and theircomplex compounds, polycarboxylic acids, 1,2-dicarboxylic anhydrides orpyromellitic dianhydride.

Polyurethane resins are derived from polyethers, polyesters andpolybutadienes with terminal hydroxyl groups, on the one hand, and fromaliphatic or aromatic polyisocyanates on the other hand.

Preferably, the polyurethanes are prepared in situ from polyethers,polyesters and polybutadienes with terminal hydroxyl groups, on the onehand, and from aliphatic or aromatic poly-isocyanates on the other hand.

Examples of suitable polyvinyl resins are polyvinylbutyral, polyvinylacetate or copolymers thereof.

Suitable phenolic resins are synthetic resins in the course of whoseconstruction phenols are the principal component, i.e. in particularphenol-, cresol-, xylenol- and resorcinol-form-aldehyde resins,alkylphenolic resins, and condensation products of phenols withacetaldehyde, furfurol, acrolein or other aldehydes. Modified phenolicresins are also of interest.

UV-(ultraviolet) curable resins may contain one or more olefinic doublebonds. They may be of low (monomeric) or relatively high (oligomeric)molecular mass. Examples of monomers containing a double bond are alkylor hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl,butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate,methyl meth-acrylate or ethyl methacrylate. Other examples areacrylnitrile, acrylamide, methacrylamide, N-substituted(meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers suchas iso-butyl vinyl ether, styrene, alkylstyrenes and halostyrenes,N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.

Examples of monomers containing two or more double bonds are ethyleneglycol, propylene glycol, neopentyl glycol, hexamethylene glycol andbisphenol A diacrylates, 4,4′-bis(2-acryloyloxyethoxy)diphenylpropane,trimethylolpropane triacrylate, pentaerythritol triacrylate ortetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate,diallyl phthalate, triallyl phosphate, triallyl isocyanurate ortris(2-acryloylethyl)isocyanurate.

Examples of relatively high molecular mass (oligomeric) polyunsaturatedcompounds are acrylated epoxy resin and acrylated or vinyl ether- orepoxy-functional polyesters, polyurethanes and polyethers. Furtherexamples of unsaturated oligomers are unsaturated polyester resins,generally prepared from maleic acid, phthalic acid and one or more diolsand having molecular weights of from about 500 to 3000. In addition tothese it is also possible to use vinyl ether monomers and oligomers, andalso maleate-terminated oligomers with poly-esters, polyurethane,polyether, polyvinyl ether and epoxide main chains. Especially suitableare combinations of polymers and oligomers which carry vinyl ethergroups, as described in WO-A-90/01512. Also suitable, however, arecopolymers of monomers functionalized with maleic acid and vinyl ether.

Also suitable are compounds containing one or more free-radicallypolymerizable double bonds. In these compounds the free-radicallypolymerizable double bonds are preferably in the form of (meth)acryloylgroups. (Meth)acryloyl and, respectively, (meth)acrylic here and belowmeans acryloyl and/or methacryloyl, and acrylic and/or methacrylic,respectively. Preferably, at least two polymerizable double bonds arepresent in the molecule in the form of (meth)acryloyl groups. Thecompounds in question may comprise, for example,(meth)acryloyl-functional oligomeric and/or polymeric compounds ofpoly(meth)acrylate. The number-average molecular mass of this compoundmay be for example from 300 to 10 000, preferably from 800 to 10 000.The compounds preferably containing free-radically polymerizable doublebonds in the form of (meth)acryloyl groups may be obtained by customarymethods, for example by reacting poly(meth)acrylates with (meth)acrylicacid. These and other preparation methods are described in theliterature and are known to the person skilled in the art. Unsaturatedoligomers of this kind may also be referred to as prepolymers.

Functionalized acrylates are also suitable. Examples of suitablemonomers which are normally used to form the backbone (the base polymer)of such functionalized acrylate and methacrylate polymers are acrylate,methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate,isobutyl meth-acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylateetc. Additionally, appropriate amounts of functional monomers arecopolymerized during the polymerization in order to give the functionalpolymers. Acid-functionalized acrylate or methacrylate polymers areobtained using acid-functional monomers such as acrylic acid andmethacrylic acid. Hydroxy-functional acrylate or methacrylate polymersare formed from hydroxy-functional monomers, such as 2-hydroxyethylmethacrylate, 2-hydroxypropyl methacrylate and 3,4-dihydroxybutylmethacrylate. Epoxy-functionalized acrylate or methacrylate polymers areobtained using epoxy-functional monomers such as glycidyl methacrylate,2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate,2,3-epoxycyclohexyl methacrylate, 10,11-epoxyundecyl methacrylate etc.Similarly, for example, isocyanate-functionalized polymers may beprepared from isocyanate-functionalized monomers, such asmeta-isopropenyl-α,α-dimethylbenzyl isocyanate, for example.

Particularly suitable compounds are, for example, esters ofethylenically unsaturated mono-functional or polyfunctional carboxylicacids and polyols or polyepoxides, and polymers containing ethylenicallyunsaturated groups in the chain or in side groups, such as unsaturatedpolyesters, polyamides and polyurethanes and copolymers thereof, alkydresins, polybutadiene and butadiene copolymers, polyisoprene andisoprene copolymers, polymers and co-polymers containing (meth)acrylicgroups in side chains, and also mixtures of one or more such polymers.

Examples of suitable monofunctional or polyfunctional unsaturatedcarboxylic acids are acrylic acid, methacrylic acid, crotonic acid,itaconic acid, cinnamic acid, maleic acid, fumaric acid, unsaturatedfatty acids such as linolenic acid or oleic acid. Acrylic acid andmethacrylic acid are preferred.

It is, however, also possible to use saturated dicarboxylic orpolycarboxylic acids in a mixture with unsaturated carboxylic acids.Examples of suitable saturated dicarboxylic or polycarboxylic acidsinclude tetrachlorophthalic acid, tetrabromophthalic acid, phthalicacid, trimellitic acid, heptanedicarboxylic acid, sebacic acid,dodecanedicarboxylic acid, hexahydrophthalic acid, etc.

Suitable polyols include aromatic and especially aliphatic andcycloaliphatic polyols. Preferred Examples of aromatic polyols arehydroquinone, 4,4′-dihydroxybiphenyl, 2,2-di(4-hydroxyphenyl)propane,and also novolaks and resols. Examples of polyepoxides are those basedon the aforementioned polyols, especially the aromatic polyols, andepichlorhydrin. Further suitable polyols include polymers and copolymerscontaining hydroxyl groups in the polymer chain or in side groups, suchas polyvinyl alcohol and copolymers thereof or poly-hydroxyalkylmethacrylates or copolymers thereof, for example. Oligoesters containinghydroxyl end groups are further suitable polyols.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving preferably from 2 to 12 carbon atoms, such as ethylene glycol,1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol,hexanediol, octanediol, dodecanediol, diethylene glycol, triethyleneglycol, polyethylene glycols having molecular weights of preferably from200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may have been partly or fully esterified with one or moredifferent unsaturated carboxylic acids, the free hydroxyl groups inpartial esters possibly having been modified, e.g. etherified oresterified with other carboxylic acids. Examples of such esters are forexample trimethylolpropane triacrylate, trimethylolethane triacrylate,trimethylolpropane tri-methacrylate, trimethylolethane trimethacrylate,tetramethylene glycol dimethacrylate, tri-ethylene glycoldimethacrylate, tetraethylene glycol diacrylate, pentaerythritoldiacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol diacrylate, dipentaerythritol triacrylate,dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate,pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,tripentaerythritol octamethacrylate, pentaerythritol diitaconate,dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate,dipentaerythritol hexaitaconate, ethylene glycol diacrylate,1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldiitaconate, sorbitol triacrylate, sorbitol tetraacrylate, modifiedpentaerythritol triacrylate, sorbitol tetramethacrylate, sorbitolpentaacrylate, sorbitol hexaacrylate, oligoester acrylates andmethacrylates, glycerol diacrylate and triacrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycolhaving a molecular weight from 200 to 1500, or mixtures thereof.

Suitable UV-curable resins include the amides of identical or differentunsaturated carboxylic acids with aromatic, cycloaliphatic and aliphaticpolyamines having preferably from 2 to 6, particularly from 2 to 4 aminogroups. Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- ordi(β-aminopropoxy)ethane. Further suitable polyamines are polymers andcopolymers containing possibly additional amino groups in the sidechain, and oligoamides having amino end groups. Examples of suchunsaturated amides are: methylenebisacrylamide,1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide,bis(methacrylamidopropoxy)ethane, β-methacrylamidoethyl methacrylate,and N-[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and diols or diamines. The maleic acid may have beenreplaced in part by other dicarboxylic acids. They may be used togetherwith ethylenically unsaturated comonomers, e.g. styrene. The polyestersand polyamides may also be derived from dicarboxylic acids andethylenically unsaturated diols or diamines, especially from relativelylong chain ones having, for example, from 6 to 20 carbon atoms. Examplesof polyurethanes are those synthesized from saturated or unsaturateddiisocyanates and unsaturated or saturated diols, respectively.

Polybutadiene and polyisoprene and copolymers thereof are known.Examples of suitable comonomers are olefins such as ethylene, propene,butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinylchloride. Polymers containing (meth)acrylate groups in the side chainare likewise known. They may comprise, for example, reaction products ofnovolak-based epoxy resins with (meth)acrylic acid, homopolymers orcopolymers of vinyl alcohol or the hydroxyalkyl derivatives thereof thathave been esterified with (meth)acrylic acid, or homopolymers andcopolymers of (meth)acrylates esterified withhydroxyalkyl(meth)acrylates.

The UV-curable resins may be used alone or in any desired mixtures.Preference is given to using mixtures of polyol (meth)acrylates.

It is also possible to add binders to the compositions of the invention,which is especially appropriate when the photopolymerizable compoundsare liquid or viscous substances. The amount of the binder can be forexample 5-95, preferably 10-90 and especially 40-90% by weight, based onthe overall solids. The choice of binder is made depending on the fieldof use and the properties required for that field, such asdevelopability in aqueous and organic solvent systems, adhesion tosubstrates, and oxygen sensitivity, for example.

The unsaturated compounds may also be used in a mixture withnon-photopolymerizable film-forming components. These may be, forexample, physically drying polymers or their solutions in organicsolvents, such as nitrocellulose or cellulose acetobutyrate, forexample. They may also, however, be chemically and/or thermally curableresins, such as polyiso-cyanates, polyepoxides or melamine resins, forexample. By melamine resins are meant not only condensates of melamine(1,3,5-triazine-2,4,6-triamine) but also those of melamine derivatives.In general, the components comprise a film-forming binder based on athermo-plastic or thermosettable resin, predominantly on athermosettable resin. Examples thereof are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.The additional use of thermally curable resins is of importance for usein what are known as hybrid systems, which may be both photopolymerizedand also thermally crosslinked.

Component (a) may comprise, for example, a coating compositioncomprising (a1) compounds containing one or more free-radicallypolymerizable double bonds and further containing at least one otherfunctional group which is reactive in the sense of an addition reactionand/or condensation reaction (examples have been given above), (a2)compounds containing one or more free-radically polymerizable doublebonds and further containing at least one other functional group whichis reactive in a sense of an addition reaction and/or condensationreaction, the additional reactive functional group being complementaryto or reactive toward the additional reactive functional groups ofcomponent (a1), (a3) if desired, at least one monomeric, oligomericand/or polymeric compound containing at least one functional group whichis reactive in the sense of an addition reaction and/or condensationreaction toward the functional groups from component (a1) or component(a2) that are present in addition to the free-radically polymerizabledouble bonds.

Component (a2) carries in each case the groups which are reactive towardor complementary to component (a1). In this context it is possible ineach case for different kinds of functional groups to be present in onecomponent. In component (a3) there is a further component availablecontaining functional groups which are reactive in the sense of additionreactions and/or condensation reactions and which are able to react withthe functional groups of (a1) or (a2) that are present in addition tothe free-radically polymerizable double bonds. Component (a3) containsno free-radically polymerizable double bonds. Examples of suchcombinations of (a1), (a2), (a3) can be found in WO-A-99/55785. Examplesof suitable reactive functional groups are selected, for example, fromhydroxyl, isocyanate, epoxide, anhydride, carboxyl or blocked aminogroups. Examples have been described above.

In addition, the following coating systems are of interest as component(a) of the coating compositions:

1. surface coatings based on cold- or hot-crosslinkable alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins,optionally with the addition of a curing catalyst;2. two-component polyurethane surface coatings based onhydroxyl-group-containing acrylate, polyester or polyether resins andaliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;3. two-component polyurethane surface coatings based onthiol-group-containing acrylate, polyester or polyether resins andaliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;4. one-component polyurethane surface coatings based on blockedisocyanates, isocyanurates or polyisocyanates which are deblocked duringstoving; the addition of melamine resins is also possible, if desired;5. one-component polyurethane surface coatings based on aliphatic oraromatic urethanes or polyurethanes and hydroxyl-group-containingacrylate, polyester or polyether resins;6. one-component polyurethane surface coatings based on aliphatic oraromatic urethane acrylates or polyurethane acrylates having free aminegroups in the urethane structure and melamine resins or polyetherresins, optionally with the addition of a curing catalyst;7. two-component surface coatings based on (poly)ketimines and aliphaticor aromatic isocyanates, isocyanurates or polyisocyanates;8. two-component surface coatings based on (poly)ketimines and anunsaturated acrylate resin or a polyacetoacetate resin or amethacrylamidoglycolate methyl ester;9. two-component surface coatings based on carboxyl- oramino-group-containing polyacrylates and polyepoxides;10. two-component surface coatings based on anhydride-group-containingacrylate resins and a polyhydroxy or polyamino component;11. two-component surface coatings based on acrylate-containinganhydrides and poly-epoxides;12. two-component surface coatings based on (poly)oxazolines andanhydride-group-containing acrylate resins or unsaturated acrylateresins or aliphatic or aromatic isocyanates, isocyanurates orpolyisocyanates;13. two-component surface coatings based on unsaturated (poly)acrylatesand (poly)-malonates;14. thermoplastic polyacrylate surface coatings based on thermoplasticacrylate resins or extrinsically crosslinking acrylate resins incombination with etherified melamine resins;15. surface-coating systems, especially clearcoats, based onmalonate-blocked isocyanates with melamine resins (e.g.hexamethoxymethylmelamine) as crosslinkers (acid-catalysed);16. UV-curable systems based on oligomeric urethane acrylates and/oracylate acrylates, optionally with the addition of other oligomers ormonomers;17. dual-cure systems, which are cured first thermally and then by UV,or vice versa, the constituents of the surface-coating formulationcontaining double bonds that can be caused to react by UV light andphotoinitiators and/or by electron-beam curing.Furthermore, there come into consideration coating systems which arebased on siloxanes. Such coating systems are described, for example, inWO-A-98/56852, WO-A-98/56853, DE-A-2914427 and DE-A-4338361.

Component (b) can also find use in resists, micro resists or soldermasks for printed circuit boards, especially for improving the scratchresistance thereof.

Preferably, component (b) is added to the material to be stabilized,compatibilized, flame-retarded and/or polymerization regulated in anamount from 0.01 to 80%, in particular 1 to 50%, for example 2 to 20%,relative to the weight of the organic material to be stabilized,compatibilized, flame-retarded and/or polymerization regulated.

In general, the compositions according to the invention can contain, inaddition to components (a) and (b), additional additives, for example,from the group consisting of pigments, dyes, fillers, flow controlagents, dispersants, thixotropic agents, adhesion promoters,antioxidants, light stabilizers and curing catalysts such as, forexample, the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutyl phenol, 2,6-dicyclopentyl-4-methyl phenol,2-(α-methylcyclohexyl)-4,6-dimethyl-phenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-meth-oxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethyl phenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methyl phenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methyl phenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methyl phenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methyl phenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methyl phenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethyl benzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-azine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or poly-hydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N, N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic Acid (Vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyidiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylamino-methylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetra-methyl-4,4′-diaminodiphenyl methane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl-amino)propane, (o-tolyl)biguanide,bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylatedN-phenyl-1-naphthylamine, a mixture of mono- and dialkylatedtert-butyl/tert-octyidiphenylamines, a mixture of mono- and dialkylatednonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyl-diphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene.

2. UV absorbers and light stabilizers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzo-triazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-meth-oxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonyl-ethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxy-phenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂₂, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl phenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl phenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-β-methoxycinnamate, butylα-cyano-β-methyl-β-methoxy-cinnamate, methylα-carbomethoxy-β-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl indoline, neopentyltetra(α-cyano-β,β-di-phenylacrylate.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethyl hexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor(Clariant; CAS Reg. No. 106917-31-1],5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, thereaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine),1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine.

2.7. Oxamides, for example 4, 4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andβ-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydro-oxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N, N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N N′-bis(salicyloyl)oxalyl dihydrazide,N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

5. Hydroxylamines, for example N,N-dibenzyl hydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecyl hydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecyl hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyinitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone,N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone,N-ocatadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate, dimistrylthiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecyl mercapto)propionate.

9. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, car-bon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(2,3-dimethyl phenyl)-5,7-di-tert-butyl benzofuran-2-one,3-(2-acetyl-5-isooctyl phenyl)-5-isooctylbenzofuran-2-one.

The additional additives are added, for example, in concentrations of0.01 to 10%, relative to the total weight of the material to bestabilized, flame protected and/or compatibilized.

In general, incorporation of component (b) and, if desired, furtheradditives into the polymeric, organic material is carried out by knownmethods, for example before or during moulding or else by applying thedissolved or dispersed compounds to the polymeric, organic material, ifappropriate with subsequent slow evaporation of the solvent. Component(b) can also be added to the materials to be stabilized in the form of amasterbatch or a colloidal sol or organosol containing for example 5 to50% by weight of component (b).

Component (b) can also be added before or during polymerisation orbefore crosslinking.

Component (b) can be incorporated into the material to be stabilizedand/or compatibilized in pure form or encapsulated in waxes, oils orpolymers.

Component (b) can also be sprayed onto the material to be stabilized,compatibilized, flame-retarded and/or polymerized.

The materials thus treated as mentioned above can be used in variousforms, for example as films, fibres, ribbons, moulded materials,profiles, coatings or as binders for paints, adhesives or cement.

The present invention further provides a process for stabilizing,flame-retarding and/or compatibilizing an organic material which issubject to oxidative, thermal or light-induced degradation, whichcomprises incorporating therein, or applying thereto, at least afunctionalized nanoparticle of the present invention comprising on thesurface at least a radical of the formula I and optionally a radical ofthe formula II.

The present invention also provides a process for photoinitiatingin-situ polymerization or hardening of a pre-polymeric nanocomposite orsol to a nanocomposite material, which comprises incorporating therein,or applying thereto, at least a functionalized nanoparticle of thepresent invention comprising on the surface at least a radical of theformula I and optionally a radical of the formula II.

A further embodiment of the present invention is the use of afunctionalized nanoparticle of the present invention comprising on thesurface at least a radical of the formula I and optionally a radical ofthe formula II as stabilizer and/or flame-retarder and/or compatibilizerfor organic materials which are subject to oxidative, thermal orlight-induced degradation.

The present invention also provides the use of a functionalizednanoparticle of the present invention comprising on the surface at leasta radical of the formula I and optionally a radical of the formula II asphotoinitiator for the in-situ polymerization or hardening ofpre-polymeric nanocomposites or sols to nanocomposite materials.

A preferred embodiment of the present invention is also the use ofcomponent (b) as reinforcer of coatings and improver of scratchresistance in coating compositions for surfaces.

The present invention also relates to a process for protecting asubstrate, which comprises applying thereto a coating compositioncomprising components (a) and (b) and then drying and/or curing it.

The present invention likewise relates to a process for preparing areinforced coating with improved scratch resistance on a surface, whichcomprises treating this surface with a coating composition comprisingcomponents (a) and (b), and then drying and/or curing it.

The preferred functionalized nanoparticles and organic materials for theprocess and use are the same as those for the compositions according tothe invention.

The following Examples illustrate the invention in more detail. Parts orpercentages are by weight.

EXAMPLE 1 Preparation of 3-aminopropylsilane Modified SilicaNanoparticles

510 g of Ludox TMA (RTM) [available from Helm AG; 34% nanosilicadispersion in water] is mixed with 2490 g of ethanol. 345 g3-aminopropyl-trimethoxysilane (Fluka purum) is added dropwise to thishomogeneous mixture. After the addition, the mixture is heated at 50° C.for 18 hours. The volume of this mixture is then reduced to ca. 1 literby evaporating ethanol/water in the rotary evaporator. A total of 4liter of hexane is added, the mixture is shaken vigorously and the twophases separated in a separation funnel to remove unreacted aminosilane.The acqueous/ethanolic lower phase is concentrated to a wet paste in therotary evaporator in vacuo and then resuspended in 1 liter of ethanol. Atotal of 1199 g solution is obtained with a solid content of 27.3 wt. %.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 600° C.): Weight loss: 25.2% corresponding to the organic material.Elemental analysis: found: C, 17.68%, H, 4.65%, N, 6.73%: correspondingto an organic content of 28.1% in relatively good agreement to the TGAvalue. Transmission Electron Microscopy (TEM): An average diameter of35-40 nm is obtained for the individual nanoparticles. Dynamic lightscattering (DLS): Average diameter d=90-110 nm.

EXAMPLE 2 Preparation of Propylsilane and 3-aminopropylsilane ModifiedSilica Nanoparticles

50 g of Ludox TMA (RTM) [available from Helm AG, 34% nanosilicadispersion in water] is mixed with 250 ml of ethanol. Then is added amixture of 2.29 g (12.8 mmol) 3-aminopropyl-trimethoxysilane (Flukapurum) and 8.42 g (51.3 mmol) of propyltrimethoxysilane (Fluka purum)dropwise during 15 minutes with stirring. After the addition, themixture is heated at 50° C. for 16 hours. The reaction mixture iscentrifuged (1 hour, 2000 rpm) and the sedimented product redispersed in200 ml of ethanol followed by a second centrifugation (1 hour, 2000rpm). The sedimented product is re-dispersed in 70 ml toluene to give adispersion with a solid content of 13.5 wt. %. Thermographimetricanalysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weightloss: 5.9% corresponding to the organic material. Elemental analysis:found: C, 4.70%, H, 1.22%, N, 0.37%: corresponding to an aminopropylcontent of 2.36 wt. % and a n-propyl content of 3.53 wt. %. Dynamiclight scattering (DLS): Average diameter d=69 nm.

EXAMPLE 3 Preparation of Hexadecylsilane and 3-aminopropylsilaneModified Silica Nanoparticles

138.8 g of Ludox TMA (RTM) [available from Helm AG, 34% nanosilicadispersion in water] is mixed with 1.4 liter of ethanol. Then is added amixture of 47.2 g (263.3 mmol) of 3-aminopropyltrimethoxysilane (Flukapurum) and 47.2 g (136.2 mmol) of hexadecyltrimethoxysilane (Flukapurum) and heated at 50° C. for 16 hours. The reaction mixture iscentrifuged (1 hour, 3000 rpm) and the sedimented product is redispersedin 200 ml of ethanol. This is repeated two more times. The sedimentedproduct is re-dispersed in 250 ml of xylene to give a dispersion with asolid content of 23.9 wt. %. Thermographimetric analysis (TGA; heatingrate: 10° C./min from 50° C. to 600° C.): Weight loss: 26.2%corresponding to the organic material. Elemental analysis: found: C,17.43%, H, 3.69%, N, 1.81%: corresponding to an aminopropyl content of7.5 wt. % and a n-propyl content of 18.7 wt. %. Dynamic light scattering(DLS): Average diameter d=97 nm.

EXAMPLE 4 Preparation of Methylsilane and 3-aminopropylsilane ModifiedSilica Nanoparticles

50 g of Ludox TMA (RTM) [available from Helm AG, 34% nanosilicadispersion in water] is mixed with 250 ml of ethanol. Then is added amixture of 2.29 g (12.8 mmol) of 3-aminopropyltrimethoxysilane (Flukapurum) and 7.0 g (51.3 mmol) of methyltrimethoxysilane (Fluka purum)dropwise during 15 min with stirring. After the addition, the mixture isheated at 50° C. for 16 hours. The reaction mixture is centrifuged (1 h,2000 rpm) and the sedimented product is re-dispersed in 200 ml ofethanol followed by a second centrifugation (1 hour, 2000 rpm). Thesedimented product is re-dispersed in 80 ml toluene to give 177.4 g of adispersion with a solid content of 10.0 wt. %. Thermographimetricanalysis (TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weightloss: 5.9% corresponding to the organic material. Elemental analysis:found: C, 3.96%, H, 1.20%, N, 0.67%: corresponding to an aminopropylcontent of 2.77 wt. % and a methyl content of 3.08 wt. %.

EXAMPLE 5 Preparation of UV-Absorber and HALS Modified SilicaNanoparticles

20 g of the dispersion according to Example 1 is concentrated with therotary evaporator to a wet paste and redispersed in 20 ml ofdimethylacetamide. 3.92 g (13.1 mmol) of the HALS-acrylate [see reactionscheme; prepared from the 4-hydroxy HALS derivative by acylation withacryloylchloride] dissolved in 80 ml of dimethylacetamide and 7.75 g(13.1 mmol) of the UV-absorber acrylate [see reaction scheme] dissolvedin 20 ml of dimethylacetamide is added and the mixture stirred at 50° C.for 19 hours. The reaction mixture is concentrated in the rotaryevaporator to about half the volume and 800 ml of ethanol is added whichleads to the precipitation of the modified particles. The product isisolated by centrifugation (20 minutes at 2000 rpm) and the sedimentedproduct redispersed in 60 ml toluene. Yield: 100 g dispersion with 12.3wt. % solid content. Thermographimetric analysis (TGA; heating rate: 10°C./min from 50° C. to 800° C.): Weight loss: 73.0% corresponding to theorganic material. Elemental analysis: found: C, 52.53%, H, 5.61%, N,6.27%: corresponding to an organic content of 73.9% in relatively goodagreement to the TGA value. Dynamic light scattering (DLS): Averagediameter d=100 nm.

EXAMPLE 6 Preparation of UV-Absorber and HALS Modified SilicaNanoparticles

20 g of the dispersion according to Example 1 is concentrated with therotary evaporator to a wet paste and redispersed in 20 ml ofdimethylacetamide. 3.98 g (13.3 mmol) of the HALS-acrylate [see reactionscheme; prepared from the 4-hydroxy HALS derivative by acylation withacryloylchloride] dissolved in 20 ml of dimethylacetamide and 6.59 g(13.3 mmol) of the UV-absorber acrylate [see reaction scheme] dissolvedin 60 ml of dimethylacetamide is added and the mixture stirred at 50° C.for 18 hours. The reaction mixture is concentrated in the rotaryevaporator to about half the volume and 400 ml of ethanol is added whichleads to the precipitation of the modified particles. The product isisolated by centrifugation (1 hour, 2000 rpm) and the sedimented productredispersed in 70 ml of toluene. Yield: 74.1 g dispersion with 15.7 wt.% solid content. Thermographimetric analysis (TGA; heating rate: 10°C./min from 50° C. to 800° C.): Weight loss: 71.4% corresponding to theorganic material. Elemental analysis: found: C, 49.20%, H, 5.83%, N,6.60%: corresponding to an organic content of 71.0% in good agreement tothe TGA value. Dynamic light scattering (DLS): Average diameter d=99 nm.

EXAMPLE 7 Preparation of Hydroxyether Modified Silica Nanoparticles

100 g of the dispersion according to Example 1 is mixed with 13.9 g(120.5 mmol) of glycidyl-isopropylether (Fluka, purum) and stirred at50° C. for 18 h. The mixture is concentrated in the rotary evaporator togive 38.05 g of a paste. The product is re-dispersed in all kind oforganic solvents (e.g. toluene). Thermographimetric analysis (TGA;heating rate: 10° C./min from 50° C. to 600° C.): Weight loss: 50.2%corresponding to the organic material. Elemental analysis: found: C,34.23%, H, 6.55%, N, 4.22%: corresponding to an organic content of54.7%.

EXAMPLE 8 Preparation of UV-Absorber and Hydroxyether Modified SilicaNanoparticles

19.28 g of the dispersion according to Example 1 is mixed with 1.25 g(10.8 mmol) of glycidyl-isopropylether (Fluka, purum) and stirred at 50°C. for 18 hours. The mixture is concentrated in the rotary evaporator toa wet paste and re-dispersed in 28.2 g of dimethylacetamide. 5.35 g(10.8 mmol) of the UV-absorber acrylate [see reaction scheme] isdissolved in 74 g of dimethylacetamide is added and the mixture stirredat 50° C. for 20 hours. 500 ml of ethanol is added which leads to theprecipitation of the modified particles. The product is isolated bycentrifugation (1 hour, 2000 rpm) and the sedimented product redispersedin 30 g toluene. Yield: 57.3 g dispersion with 14.7 wt. % solid content.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 54.4% corresponding to the organic material.Elemental analysis: found: C, 44.35%, H, 5.30%, N, 6.12%: correspondingto an organic content of 64.9%. Dynamic light scattering (DLS): Averagediameter d=107 nm.

EXAMPLE 9 Preparation of Antioxidant Modified Silica Nanoparticles

100 g (342 mmol) of methylox (commercial product of Ciba SpecialtyChemicals) is melted at 100° C. and 0.3 g of dibutyltinoxide is added.Thereafter, 61.26 g of the dispersion according to Example 1 is addeddropwise to this mixture during 45 minutes with good stirring, wherebyethanol is distilled off. The temperature is then rised to 130° C. andkept at there for 15 hours. The reaction mixture is cooled to 60° C. anddiluted with 1.5 liter of cyclohexane which leads to the precipitationof the modified particles. The product is isolated by centrifugation (20minutes, 2000 rpm) and the sedimented product re-dispersed in 60 ml ofxylene. Yield: 89.7 g dispersion with 13 wt. % solid content.Thermographimetric analysis (TGA; heating rate: 10° C./minute from 50°C. to 600° C.): Weight loss: 39% corresponding to the organic material.Elemental analysis: found: C, 30.72%, H, 4.24%, N, 2.06%: correspondingto an organic content of 43.1%. TEM: Average diameter d=28 nm.

EXAMPLE 10 Preparation of Antioxidant Modified Silica Nanoparticles (SeeReaction Scheme in Example 9)

85.54 g (216.8 mmol) of Irganox 3052 FF (commercial product of CibaSpecialty Chemicals) is dissolved in 260 g of xylene at 50° C. and 200 gof the dispersion according to Example 1 is added. The mixture isstirred at 50° C. for 17 hours. All the solvent is evaporated in therotary evaporator and the solid product dried in vacuo at 50° C. 143 gof a white powder is obtained. Thermographimetric analysis (TGA; heatingrate: 10° C./min from 50° C. to 600° C.): Weight loss: 72.1%corresponding to the organic material. Elemental analysis: found: C,58.05%, H, 7.47%, N, 2.33%: corresponding to an organic content of75.4%. TEM: Average diameter d=21 nm.

EXAMPLE 11 Preparation of Polyethyleneglycol Modified SilicaNanoparticles

To 60 g of the dispersion according to Example 1 is added 35.91 g (79.1mmol) of poly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at room temperature. The mixture is stirredat 50° C. for 22 hours. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. The product verified by ¹H-NMRthat there are no residual acrylic double bonds left. The product isthan dispersed in 150 ml acetic acid butyl ester to give 199.5 g of adispersion with 26.35 wt. % solid content. Thermographimetric analysis(TGA; heating rate: 10° C./min from 50° C. to 600° C.): Weight loss:74.9%, corresponding to the organic material. Elemental analysis: found:C, 42.79%, H, 7.46%, N, 2.09%: corresponding to an organic content of74.2%. DLS: Average diameter d=151 nm.

EXAMPLE 12 Preparation of Caprolactone Modified Silica Nanoparticles

To 60 g of the dispersion prepared according to Example 1 is added 27.21g (79.1 mmol) of Sartomer SR 495 (MW=344) at room temperature. Themixture is stirred at 50° C. for 22 hours. The solvent is evaporated inthe rotary evaporator to obtain a transparent oil. The product isverified by ¹H-NMR that there are no residual acrylic double bonds left.The pro-duct is than dispersed in 130 ml acetic acid butyl ester to give181.2 g of a dispersion with 24.7 wt. % solid content.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 600° C.): Weight loss: 72.2%, corresponding to the organic material.Elemental analysis: found: C, 43.71%, H, 6.94%, N, 2.45%: correspondingto an organic content of 71.8%. DLS: Average diameter d=80-120 nm.

EXAMPLE 13 Preparation of Hindered Amine Light Stabilizer ModifiedSilica Nanoparticles

To 66.3 g of the dispersion prepared according to Example 1 is added17.9 g (80.3 mmol) of a HALS-acrylate derivative [prepared by acylationof 4-hydroxy-1,2,2,6,6-pentamethyl-piperidine with acryloylchloride] in60 ml of ethanol at room temperature. The mixture is stirred at 50° C.for 20 hours. The amount of solvent is halved by evaporation in therotary evaporator. By adding 100 ml of hexane the product precipitatesand is separated by centrifugation. After re-dispersing the product inacetic acid butyl ester (BuOAc) a dispersion with 6.2 wt. % solidcontent is obtained. The product is verified by ¹H-NMR that there are noresidual acrylic double bonds left. Thermographimetric analysis (TGA;heating rate: 10° C./min from 25° C. to 600° C.): Weight loss: 19.2%,corresponding to the organic material. Elemental analysis: found: C,11.45%, H, 2.16%, N, 1.98%: corresponding to an organic content of17.3%. DLS: Average diameter d=107 nm.

EXAMPLE 14 Preparation of Photoinitiator and Propyl MethacrylateModified Silica Nanoparticles

100 g of Ludox TMA (RTM) [available from Helm AG; 34% nanosilicadispersion in water] is mixed with 100 ml of ethanol. To this mixture isadded 11.7 g (25.6 mmol) of a photoinitiator [see reaction scheme] and12.7 g (51 mmol) of 3-(trimethoxysilyl)propyl methacrylate at roomtemperature. The mixture is stirred at 50° C. for 20 houry. The amountof solvent is halved by evaporation in the rotary evaporator. By adding150 ml of cyclohexane the product precipitates and is separated bycentrifugation. After re-dispersing the product in butylacetate (BuOAc)a dispersion with 18.6 wt. % solid content is obtained. The ratio ofphotoinitiator to methacrylic groups is calculated based on analyticaldata to be 1 to 1.54. Thermographimetric analysis (TGA; heating rate:10° C./min from 25° C. to 600° C.): Weight loss: 28.6%, corresponding tothe organic material. Elemental analysis: found: C, 18.68%, H, 2.64%, O:9.52%, S: 1.72: corresponding to an organic content of 32.6%. DLS:Average diameter d=54 nm.

EXAMPLE 15 Preparation of UV-Absorber and Poly(Ethylenglycol)Methylether(Mpeg) Modified Silica Nanoparticles

50 g of Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml ofethanol. To this mixture is added 22 g (51 mmol) ofpolyethyleneglycolmethylether triethoxysilane [independently preparedfrom poly(ethyleneglycol)methylether methacrylate (CAS 26915-72-0,Laporte Performance Chemicals, MW=430 g/mol) by Michael addition with3-aminopropyl triethoxysilane] and 12.8 g (25.6 mmol) of the UV absorber[independently prepared from the benztriazole derivative and3-aminopropyl triethoxysilane by amidization reaction] at roomtemperature. The mixture is stirred at 50° C. for 20 hours. The productprecipitates from the reaction mixture and is separated by furthercentrifugation. After re-dispersing the product in butylacetate (BuOAc)a dispersion with 8.2 wt. % solid content is obtained.Thermographimetric analysis (TGA; heating rate: 10° C./min from 25° C.to 600° C.): Weight loss: 29.7%, corresponding to the organic material.Elemental analysis: found: C, 17.31%, H, 2.82%, N, 2.49: correspondingto an organic content of 30.4%. DLS: Average diameter d=115 nm.

EXAMPLE 16 Preparation of Photoinitiator and Octyl Modified SilicaNanoparticles

100 g of Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml ofethanol. To this mixture is added 4.4 g (9.6 mmol) of the photoinitiatortrimethoxysilane [see Example 11 and scheme above] and 16.6 g (67.3mmol) of octyl trimethoxysilane [CAS 2943-75-1, purum >97% GC, Fluka] atroom temperature. The mixture is stirred at 50° C. for 20 hours. Byadding 150 ml of hexane the product precipitates and is separated bycentrifugation. After re-dispersing the product in xylene a dispersionwith 28 wt. % solid content is obtained. Thermographimetric analysis(TGA; heating rate: 10° C./min from 25° C. to 600° C.): Weight loss:19.7%, corresponding to the organic material. Elemental analysis: found:C, 12.79%, H, 2.18%, O: 2.85%, S: 0.69%: corresponding to an organiccontent of 18.51%. DLS: Average diameter d=33 nm.

EXAMPLE 17 Preparation of UV-Absorber andPoly(Ethyleneglycol)Methylether (Mpeg) Modified Silica Nanoparticles

7.5 g (15 mmol) of the UV-absorber acrylate (see scheme above for thestructural formula) is dissolved in 120 ml dimethylacetamide (DMA). Tothis solution is added at room temperature 34 g (75 mmol) ofMPEG(8)acrylate [poly(ethyleneglycol)methylether acrylate, CAS32171-39-4, Aldrich, MW=454 g/mol] and 60 g of the dispersion accordingto Example 1. The reaction mixture is stirred at 50° C. for 15 hours.The solvent is evaporated in the rotary evaporator to give a yellow oil.The product is verified by ¹H-NMR that there are no residual acrylicdouble bonds left. The product is than dispersed in 35 ml of xylene togive 72 g of a dispersion with 47.2 wt. % solid content.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 73%, corresponding to the organic material.Elemental analysis: found: C, 44.2%, H, 6.2%, N, 4.7%, O: 14.6%:corresponding to an organic content of 70%. DLS: Average diameter d=310nm.

EXAMPLE 18 Preparation of Photoinitiator andPoly(Ethylenglycol)Methylether (Mpeg) Modified Silica Nanoparticles

4.2 g (15 mmol) of the photoinitiator acrylate (see scheme above for thestructural formula) is dissolved in 50 ml of ethanol. Then is added 34 g(75 mmol) of MPEG(8)acrylate [poly(ethyleneglycol)methylether acrylate,CAS 32171-39-4, Aldrich, MW=454 g/mol] and 60 g of the dispersionaccording to Example 1 at room temperature. The reaction mixture isstirred at 50° C. for 15 hours. The solvent is evaporated in the rotaryevaporator to give a colourless oil. The product is verified by ¹H-NMRthat there are no residual acrylic double bonds left. The product isthen dispersed in 35 ml of butyl acetate (BuOAc) to give 64 g of adispersion with 48.8 wt. % solid content is obtained. Thermographimetricanalysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weightloss: 76.9%, corresponding to the organic material. Elemental analysis:found: C, 44.7%, H, 6.4%, N, 2.6%, O: 22.4%: corresponding to an organiccontent of 76.1%. DLS: Average diameter d=250 nm.

EXAMPLE 19 Preparation of Antioxidant andPoly(Ethyleneglycol)Methylether (Mpeg) Modified Silica Nanoparticles

5.9 g (15 mmol) of the antioxidant Irganox 3052 (RTM) [commercialproduct of Ciba Specialty Chemicals] is dissolved in 50 ml of xylene.Then is added at room temperature 34 g (75 mmol) of MPEG(8)acrylate[poly(ethyleneglycol)methylether acrylate, CAS 32171-39-4, Aldrich,MW=454 g/mol] and 60 g of the dispersion according to Example 1. Thereaction mixture is stirred at 50° C. for 15 hours. The solvent isevaporated in the rotary evaporator to give a yellow oil. The product isverified by ¹H-NMR that there are no residual acrylic double bonds left.The product is then dispersed in 50 ml butyl acetate (BuOAc) to give 80g of a dispersion with 41.3 wt. % solid content. Thermographimetricanalysis (TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weightloss: 76.2%, corresponding to the organic material. Elemental analysis:found: C: 48.§%, H, 6.1%, N, 2.2%, O: 16.2%: corresponding to an organiccontent of 72.6%. DLS: Average diameter d=260 nm.

EXAMPLE 20 Preparation of HALS and Poly(Ethyleneglycol)Methylether(Mpeg) Modified Silica Nanoparticles

3.4 g (15 mmol) of HALS (see reaction scheme above for structuralformula), 34 g (75 mmol) of MPEG(8)acrylate[poly(ethyleneglycol)methylether acrylate, CAS 32171-39-4, Aldrich,MW=454 g/mol] and 60 g of the dispersion according to Example 1 aremixed at room temperature. The reaction mixture is stirred at 50° C. for15 hours. The solvent is evaporated in the rotary evaporator to give ayellow oil. The product is verified by ¹H-NMR that there are no residualacrylic double bonds left. The product is then dispersed in 50 ml butylacetate (BuOAc) to give 80 g of a dispersion with 41.3 wt. % solidcontent. Thermographimetric analysis (TGA; heating rate: 10° C./min from50° C. to 800° C.): Weight loss: 74.8%, corresponding to the organicmaterial. Elemental analysis: found: C, 43.4%, H, 7.3%, N, 2.4%, O:18.9%: corresponding to an organic content of 72.4%. DLS: Averagediameter d=151 nm.

EXAMPLE 21 Preparation of Poly(N-Butyl Acrylate) Modified SilicaNanoparticles

To 200 g of the dispersion prepared according to Example 1 in ethanol,80.0 g (38 mmol) of poly(n-butyl acrylate) macromonomer with acrylateendgroup [synthesized with ATRP technology according to A. Muhlebach, F.Rime J. Polym. Sci., Polym. Chem. Ed., 2003, 41, 3425; Mn=2100, Mw=2940]is added and the reaction mixture stirred at 50° C. for 18 hours. Thevolume of this reaction mixture is then reduced to ca. 50 ml byevaporating ethanol/H₂O in the rotary evaporator. A total of 200 ml ofhexane is added, the mixture shaken vigorously and the two phasesseparated. The acqueous/ethanolic lower phase is concentrated to a wetpaste in the rotary evaporator in vacuo and then re-suspended in 350 mlEtOH to give 506 g of a solution with a solid content of 25.7 wt. %.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 21.5% corresponding to the organic material.Elemental analysis: found: C, 11.47%, H, 2.43%, N, 2.70%: correspondingto an organic content of 18%. Dynamic light scattering (DLS): Averagediameter d=64.5 nm.

EXAMPLE 22 Preparation of HALS Modified Silica Nanoparticles

100 g of Ludox TMA (RTM) dispersion (Aldrich) is mixed with 100 ml ofethanol. To this mixture is added 16.7 g (67.3 mmol) of3-methacryloyloxypropyl)-trimethoxysilane [Silan A 174, CAS 2530-85-0,purum 99% GC, Fluka] and the mixture is stirred at 50° C. for 22 hours.By adding 150 ml of hexane the product precipitates and is separated bycentrifugation. After re-dispersing the product in 200 ml of xylene 11.4g (67.3 mmol) 1,2,2,6,6-pentamethyl-4-amino-piperidine (GC purity: 92%)is added and the mixture stirred at 50° C. for 20 hours. A dispersion ofHALS modified silica nanoparticles with 25 wt. % solid content isobtained. DLS: d=47 nm. Thermographimetric analysis (TGA; heating rate:10° C./min from 25° C. to 600° C.): Weight loss: 20.1%, corresponding tothe organic material.

EXAMPLE 23 3-Aminopropylsilane Modified Alumina Nanoparticles

150 g of alumina nanoparticles (Nyacol Corp., Nyacol A120 DW, 22%nanoalumina dispersion in water) is mixed with 250 mL ethanol (EtOH). 27g 3-Aminopropyltrimethoxysilane (Fluka purum) are added dropwise to thishomogeneous mixture. After the addition, the mixture is heated to 50° C.for 15 hours. The volume of this mixture is then reduced to ca. 1 L byevaporating EtOH/H₂O in the rotary evaporator. The obtained solid isredispersed in EtOH to a 11.4 weight-% opaque dispersion.

Analytics:

Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 27.9 wt. % corresponding to the organicmaterial.

Elemental analysis: found: N, 4.16 wt. %: corresponding to an organiccontent of 17.3 wt. %. The difference between TGA and EA results is dueto the loss of water out of the inorganic matrix and water generatedfrom condensation processes on the surface during thermal treatment.

Transmission Electron Microscopy (TEM): An average diameter of 50 to 60nm is obtained for the individual primary nanoparticles.

Dynamic light scattering (DLS): Average diameter d=164 nm.

EXAMPLE 24 Polyethylene Glycol (MPEG) Modified Alumina Nanoparticles

To 50 g of a 3-aminopropylsilan modified alumina nanoparticle dispersion(solid content 6.2 wt %) (obtained according to Example 23) 4.24 g (9.3mmol) MPEG(8)acrylate (poly(ethyleneglycol)methyl ether acrylate, CAS32171-39-4, Aldrich, MW=454) is added at room temperature. The mixtureis stirred at 50° C. for 15 hours. The solvent is evaporated in therotavap to obtain a transparent resin. It was verified by ¹H-NMR thatthere are no residual acrylic double bonds left. The product is thendispersed in 100 ml BuOAc to obtain a 7.8 wt % dispersion.

Analytics:

Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 72.6 wt. % corresponding to the organicmaterial.

Elemental analysis: found: N, 1.7 wt. %, C, 36.4 wt %, H, 6.7 wt %.

Dynamic light scattering (DLS): Average diameter d=114 nm.

EXAMPLE 25 Preparation of HALS and Poly(Ethyleneglycol)Methylether(Mpeg) Modified Alumina Nanoparticles

0.39 g (1.7 mmol) of HALS (see reaction scheme above for structuralformula), 7.9 g (17.4 mmol) of MPEG(8)acrylate[poly(ethyleneglycol)methylether acrylate, CAS 32171-39-4, Aldrich,MW=454 g/mol] and 25 g of the dispersion according to Example 23 (4.3wt. % N, solid content 25 wt. %) are mixed at room temperature. Thereaction mixture is stirred at 50° C. for 15 hours. The solvent isevaporated in the rotary evaporator to give a yellow resin. The productis verified by ¹H-NMR that there are no residual acrylic double bondsleft. The product is then dispersed in butyl acetate (BuOAc) to give adispersion with 22.4 wt. % solid content. Thermographimetric analysis(TGA; heating rate: 10° C./min from 50° C. to 800° C.): Weight loss:77.8%, corresponding to the organic material. Elemental analysis: found:C, 41.3%, H, 7.0%, N, 1.7%. DLS: Average diameter d=100 nm.

EXAMPLE 26 Preparation of Antioxidant andPoly(Ethyleneglycol)Methylether (MPEG) Modified Alumina Nanoparticles

0.69 g (1.7 mmol) of the antioxidant (see reaction scheme above forstructural formula) are dissolved in 5 mL xylol and 7.9 g (17.4 mmol) ofMPEG(8)acrylate [poly(ethyleneglycol)methylether acrylate, CAS32171-39-4, Aldrich, MW=454 g/mol] and 25 g of the dispersion accordingto Example 23 (4.3 wt. % N, solid content 25 wt. %) are mixed at roomtemperature. The reaction mixture is stirred at 50° C. for 15 hours. Thesolvent is evaporated in the rotary evaporator to give a transperantresin. The product is verified by ¹H-NMR that there are no residualacrylic double bonds left. The product is then dispersed in butylacetate (BuOAc) to give a dispersion with 30.8 wt. % solid content.Thermographimetric analysis (TGA; heating rate: 10° C./min from 50° C.to 800° C.): Weight loss: 79.8%, corresponding to the organic material.Elemental analysis: found: C, 42.9%, H, 6.9%, N, 1.4%. DLS: Averagediameter d=105 nm.

EXAMPLE 27 Cinnamic Acid amide-3-propyl Trimethoxy Silane Reacted withUnmodified Silica Nanoparticles

a) Preparation of Cinnamic Acid amide-3-propyltrimethoxysilane

Solution A consisting of 10 g of cinnamic acid chloride (cinnamoylchloride, Fluka) dissolved at a temperature of 0° C. in 50 g of toluene,is run under stirring into Solution B, consisting of 12.2 g of3-amino-propyl-trimethoxysilane (APS, purum Fluka) in a mixture of 50 gof dry toluene and 60 g of dry pyridine at a temperature of 0° C. A paleyellow product precipitates and the stirring is continued for additional2 hours at a temperature of 0° C., then 12 hours at room temperature.

The reaction mixture is poured into 300 ml of deionized water, theyellow organic phase is washed and separated. After evaporation of thesolvent (toluene) in a rotary evaporator at a temperature of 40° C. (60hPa), the residual solvent is removed from the orange oil in vacuum (100hPa) at a temperature of 70° C. during 16 hours.

14.61 g of the product are obtained as orange oil (theory=18.57 g). Thestructure is confirmed by ¹H-NMR and elemental analysis:

Calculated: C, 58.22%, H, 7.49%, N, 4.53%: Si: 9.08%, O: 20.68%

found: C, 60.12%, H, 6.66%, N, 4.59%: Si: 9.20%, 0:19.43%

b) Reaction of Cinnamic Acid amide-3-propyl Trimethoxy Silane withSilica Nanoparticles

Solution C:

2 g of cinnamic acid amide-3-propyltrimethoxysilane (orange oil) aredissolved in 35 g of ethanol. This solution is added within about 5seconds under vigorously stirring to a solution of 20.3 g of Ludox TMA(colloidal silica, 34 wt. % suspension in deionized water) in 70 g ofethanol at room temperature. The milky suspension is stirred and heatedat a temperature of 50° C. for 20 hours followed by additional stirringat room temperature for 12 hours. After completion of the reaction, 80 gof n-hexane are added and stirring is continued for 2 hours tohomogenize the mixture. The suspension is centrifuged (4500 rpm) and theobtained residual is re-dispersed in 160 g of xylene, washed,centrifuged and re-dispersed thrice until no educt is found in thewashing liquid (controlled by TLC).

The white gel is separated and dispersed in xylene.

EXAMPLE 28 Preparation of Hindered Amine Light Stabilizer ModifiedSilica Nanoparticles

a) Preparation of Succinic Acid Methylesteramide-4-(2,2,6,6)-tetramethyl-1-methyl-piperidine

Solution A consisting of 2.4 g of succinic acid methylester chloride(Fluka) dissolved at a temperature of 0° C. in 10 g of tetrahydrofuran(THF), is run under nitrogen and stirring subsequent into Solution B,consisting of 3 g of 4-amino-2,2,6,6-tetramethyl-1-methyl piperidineinto a mixture of 10 g of dry tetrahydrofuran (THF) and 1 g of triethylamine at a temperature of 0° C. A white product precipitates andstirring is continued for additional 2 hours at a temperature of 0° C.,then 12 hours at room temperature.

The product containing solvent is filtered off and the white solid iswashed with 20 g of THF. The pale yellow THF-solution is evaporated fromthe solvent in a rotary evaporator at a temperature of 50° C. (65 hPa),the residual solvent is removed from the bright orange oil in vacuum(100 hPa) at a temperature of 70° C. during 16 hours.

Yield: 4.35 g, obtained as an orange paste.

The structure is confirmed by ¹H-NMR, LC-MS and IR with absorbances at1559 and 1632 cm¹.

b) Preparation of the Hindered Amine Light Stabilizer Modified SilicaNanoparticles

Solution C:

22 g of a 27.3% suspension of 3-aminopropylsilane modified silicananoparticles in ethanol are mixed with 20 g of dimethylacetamide (DMA),homogenized and the ethanol is removed with the rotary evaporator at atemperature of 50° C. (85 hPa).

This solution is added within 5 seconds under stirring to a mixtureconsisting of 0.75 g of succinic acid methylester4-amido-(2,2,6,6)-tetramethyl-1-methyl-piperidine (see example above)and 0.12 g of dibutyltinoxide dissolved in 10 g of dimethylacetamide(DMA). The milky reaction mixture is stirred and heated to a temperatureof 130° C. for 7 hours whereby methanol is distilled off. Thereafter,the mixture is cooled to room temperature and stirred for 1 hour,combined with 70 g of tetrahydrofuran (THF) and stirred for additional16 hours. The suspension is centrifuged (4500 rpm), the isolated productre-dispersed in 80 g of tetrahydrofuran, washed and centrifuged. Theobtained white gel is separated and dispersed in xylene.

Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to800° C.): Weight loss: 24.7%, corresponding to the organic material.

Elemental analysis: found: C, 15.73%, H, 3.54%, N, 5.09%.

TEM: Average diameter d=60 nm (visible core).

The IR shows a weak band at 1571 and ˜1650 cm⁻¹ corresponding to theamide-bond.

The described dispersion is finally reacted withpoly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at 50° C. for 22 hours. The suspension iscentrifugated (4500 rpm), the isolated product re-dispersed in ethanol,washed and centrifugated twice. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. It is verified by ¹H-NMR thatthere are no residual acrylic double bonds left.

To convert residual amino groups, reactions with different acrylates oranhydrides as acetic acid anhydride etc., are possible.

EXAMPLE 29 Preparation of UV-Absorber Modified Silica Nanoparticles a)Preparation of the Precursor

Solution A consisting of 2.4 g of succinic acid methyl ester chloride(Fluka) dissolved at a temperature of 0° C. in 10 g of tetrahydrofuran(THF), is run under nitrogen and stirring subsequent into Solution B,consisting of 6.37 g of the UV-absorber (indicated in the above reactionscheme) in a mixture of 10 g of dry tetrahydrofuran (THF) and 1 g oftriethylamine at a temperature of 0° C. An additional amount of 1 gtriethylamine is added and stirring is continued for additional 2 hoursat a temperature of 0° C., then 16 hours at room temperature.

The product mixture is poured into 200 ml of deionized water and the pHis adapted from 10.2 to 3.2 by addition of 3.26 g of 4% aqueoushydrochloric acid. The mixture is stirred for 40 minutes and then thepale precipitated product is filtered off and washed thrice with 200 mlof water.

The residual water is removed during 16 hours from the pale brownishproduct in vacuum at a temperature of 70° C. (100 hPa).

Yield: 7.75 g (95% of theory)

The structure is confirmed by ¹H-NMR, UV-VIS and IR spectroscopy.

Elemental analysis:

Calculated: C, 70.44%, H, 5.71%, N, 8.21%, 0:15.64%

found: C, 70.45%, H, 5.77%, N, 8.20%, 0:15.96%

b) Preparation of the UV-Absorber Modified Silica Nanoparticles

Solution C:

24 g of a 25% suspension of 3-aminopropylsilane modified silicananoparticles in ethanol are mixed with 30 g of dimethylacetamide (DMA),homogenized and the ethanol is removed with the rotary evaporator at atemperature of 50° C. (85 hPa).

This solution is added within 5 seconds under stirring to a mixtureconsisting of 0.75 g of the UV-absorber obtained as given above under a)and 0.05 g of dibutyltinoxide dissolved in 30 g of dimethylacetamide(DMA). The milky yellowish reaction mixture is stirred and heated to atemperature of 130° C. for 6 hours whereby methanol is distilled off.Thereafter, the mixture is cooled to room temperature and stirred for 1hour, combined with 140 g of tetrahydrofuran (THF) and stirred for 30minutes, then 140 g of n-hexane are added and the mixture is stirred foradditional 16 hours. The suspension is centrifugated (4500 rpm), theisolated product redispersed in 80 g of xylene, washed andcentrifugated. The obtained white gel is separated and dispersed up toten times in xylene.

Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to800° C.): Weight loss: 18.5%, corresponding to the organic material.

Elemental analysis: found: C, 12.08%, H, 2.23%, N, 2.88%.

TEM: Average diameter d=˜50 nm (visible core).

The IR shows a band at 1562 and -1644 cm⁻¹ corresponding to theamide-bond.

The described dispersion is finally reacted withpoly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at 50° C. for 22 hours. The suspension iscentrifugated (4500 rpm), the isolated product re-dispersed in ethanol,washed and centrifugated twice. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. It is verified by ¹H-NMR thatthere are no residual acrylic double bonds left.

To convert residual amino groups, reactions with different acrylates oranhydrides as acetic acid anhydride etc., are possible.

EXAMPLE 30 Preparation of Hindered Amine Light Stabilizer andPolyethyleneglycol Modified Silica Nanoparticles a) Preparation of 1:13-aminopropyl/polyethyleneglycol Modified Silica Nanoparticles

To 60 g of the dispersion according to Example 1 is added 17.94 g (39.55mmol) of poly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at room temperature. The mixture is stirredat 50° C. for 22 hours. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. It is verified by ¹H-NMR thatthere are no residual acrylic double bonds left. The product is thendispersed in ethanol to give a dispersion with 45.2 wt. % solid content.

b) Preparation of the Hindered Amine Light Stabilizer andPolyethyleneglycol Modified Silica Nanoparticles

13.3 g of a 45.2% suspension of 1:13-aminopropylsilane/MPEG-aminopropylsilane modified silica nanoparticlesin ethanol as described above under a) are mixed with 30 g ofdimethylacetamide (DMA), homogenized and the ethanol is removed with therotary evaporator at a temperature of 45° C. (70 hPa).

This solution is added within 5 seconds under stirring to a mixtureconsisting of 1 g of the hindered amine light stabilizer (succinic acidmethylester 4-amido-(2,2,6,6)-tetramethyl-1-methyl-piperidine; see theformula given in the above reaction scheme) and 60 mg of dibutyltinoxidedissolved in 20 g of dimethylacetamide (DMA). The yellowish reactionmixture is stirred and heated to a temperature of 130° C. for 5 hourswhereby methanol is distilled off. Thereafter, the mixture is cooled to50° C., combined with 140 g of tetrahydrofuran (THF) and 140 g ofn-hexane and stirred for additional 16 hours. The suspension iscentrifugated (4500 rpm), the isolated product re-dispersed in 160 g ofxylene, washed and centrifugated twice. The obtained white gel isseparated and dispersed in xylene.

Thermogravimetric analysis (TGA; heating rate: 10° C./min from 25° C. to800° C.): Weight loss: 33.9%, corresponding to the organic material.

Elemental analysis: found: C, 21.72%, H, 3.92%, N, 5.25%.

TEM: Average diameter d=˜80 nm (visible core).

The IR shows a band at 1555 and 1642 cm⁻¹ corresponding to theamide-bond.

The described dispersion is finally reacted withpoly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at 50° C. for 22 hours. The suspension iscentrifugated (4500 rpm), the isolated product re-dispersed in ethanol,washed and centrifugated twice. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. It is verified by ¹H-NMR thatthere are no residual acrylic double bonds left.

To convert residual amino groups, reactions with different acrylates oranhydrides as acetic acid anhydride etc., are possible.

EXAMPLE 31 Preparation of Hindered Amine Light Stabilizer, UV-Absorberand Polyethyleneglycol Modified Silica Nanoparticles

13.3 g of a 45.2% suspension of 1:13-aminopropylsilane/MPEG-aminopropylsilane modified silica nanoparticlein ethanol as described above are mixed with 30 g of dimethylacetamide(DMA), homogenized and the ethanol is removed with the rotary evaporatorat a temperature of 45° C. (75 hPa). This solution is added within 5seconds under stirring to a mixture consisting of 1 g of the hinderedamine light stabilizer (succinic acid methylester4-amido-(2,2,6,6)-tetramethyl-1-methyl-piperidine; see the formula givenin the above reaction scheme), 1 g of the benztriazole UV-absorber (seethe formula given in the above reaction scheme) and 120 mg ofdibutyltinoxide dissolved in 20 g of dimethylacetamide (DMA). Theyellowish reaction mixture is stirred and heated to a temperature of130° C. for 5 hours whereby methanol is distilled off. Thereafter, themixture is cooled to 50° C., combined with 200 g of tetrahydrofuran(THF) and 200 g of n-hexane and stirred for additional 16 hours. Thesuspension is centrifugated (4500 rpm), the isolated productre-dispersed in 160 g of xylene, washed and centrifugated twice. Theobtained gel is separated and dispersed in xylene.

Elemental analysis: found: C, 23.37%, H, 4.11%, N, 5.58%.

TEM: Average diameter d=˜50 nm (visible core).

The described dispersion is finally reacted withpoly(ethyleneglycol)methyl ether acrylate [MPEG(8)acrylate, CAS32171-39-4, Aldrich, MW=454] at 50° C. for 22 hours. The suspension iscentrifugated (4500 rpm), the isolated product re-dispersed in ethanol,washed and centrifugated twice. The solvent is evaporated in the rotaryevaporator to obtain a transparent oil. It is verified by ¹H-NMR thatthere are no residual acrylic double bonds left.

To convert residual amino groups, reactions with different acrylates oranhydrides as acetic acid anhydride etc., are possible.

EXAMPLE 32 Scratch Resistance of Polyurethane Coatings a) Preparation ofthe Polyol Component.

54.8 g of Macrynal SM 510n (60% supply form from Solution), 11.5 g ofbutylglycol acetate, 4.70 g of Solvesso 100 (obtained from Exxon), 5.68g of Methyl isobutyl ketone, 0.07 g of zinc octoate and 0.15 g of BYK300 (Byk-Chemie, Germany, anti-foaming agent) are mixed to give 76.9 ofthe polyol component.

b) Scratch Resistance of Polyurethane Coatings:

A specific amount (see Table 1) of surface functionalized silicananoparticle dispersions as prepared according to Examples 1-12 areincorporated into 7.7 g of the polyol component [Example 32a]. Theamount of each silica nanoparticle dispersion is calculated to be 5wt.-% SiO₂ of the final clear coat formulation. These formulations aretreated with 2.8 g of Desmo-dur N 75 (RTM) (Isocyanate from Bayer). Theresulting clear coat formulation (solids content 50%) is subsequentlyapplied as transparent topcoat at a dry film thickness of 40 μm ontosteel panels (10 cm×30 cm) precoated with a black basecoat. Afterapplication, the clear coat is cured at 120° C. for 45 minutes.

The scratch resistance of the coated panels is measured using thefollowing method: The 20° gloss of the panels is measured 48 hours aftercuring (DIN 67 530). The panels are sub-sequently exposed to scratchingby an Amtec Kistler apparatus according to DIN concept 55668 for thenumber of cycles as indicated in Table 1. The 20° gloss is measuredagain on the scratched area of each test panel. The results aresummarized in Table 1.

TABLE 1 initial gloss after gloss after Example Sample wt.-% silicagloss 10 cycles 20 cycles 32a^(a)) — — 84 76 71 32b^(b)) Example 2  5 8478 75 32c^(b)) Example 4  5 85 81 74 32d^(b)) Example 7  5 87 78 7432e^(b)) Example 13 5 86 80 78 32f^(b)) Example 15 5 86 77 76 32g^(b))Example 19 5 86 77 73 ^(a))Comparison Example. ^(b))Example according tothe invention.

EXAMPLE 33 Preparation of a Scratch Resistant Coating

The following formulation is prepared:

Wt % Ebecryl 604 (75% Epoxyacrylate in HDDA; Cytec) 89 Sartomer SR 344(Polyethylenglykol 400 Diacrylat; Cray Valley) 10 Ebecryl 350(Silikondiacrylat; Cytec) 1

20 g of the above formulation is mixed with 18 g of the dispersionobtained according to Example 14 (comprising the corresponding surfacefunctionalized silica nanoparticle). The resulting homogenizedformulation is applied to a white-based chipboard by a 150 μm slitcoater. The panel with the applied coating is placed in an oven at 40°C. for 10 minutes to evaporate the solvent, which has been incorporatedthrough the nano particle dispersion. The coatings are cured with two 80W/cm mercury medium pressure lamps at a belt speed of 5 m/min using aPPG equipment from AETEC. A hard and scratch resistant coating isobtained.

1. A functionalized nanoparticle comprising on the surface a covalentlybound radical of the formula I

wherein the nanoparticle is a SiO₂, Al₂O₃ or mixed SiO₂ and Al₂O₃nanoparticle, X is oxygen, sulfur or

R₁ is C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

hydroxyl-substituted C₂-C₂₄alkyl which is interrupted by oxygen, sulfuror

C₂-C₂₄alkenyl, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, a polymerizablegroup, a polymer, or an additive selected from the group consisting ofradical scavengers, hydroperoxide decomposers, UV-absorbers, lightstabilizers, flame retardants and photoinitiators; R₂ and R₃independently of each other are hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl whichis interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, phenyl,C₇-C₉phenylalkyl, —OR₅,

R₄ is hydrogen, C₁-C₂₅alkyl or C₃-C₂₅alkyl which is interrupted byoxygen or sulfur; R₅ is hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which isinterrupted by oxygen or sulfur; C₂-C₂₄alkenyl, phenyl,C₇-C₉phenylalkyl,

or the nanoparticle surface, R₆ and R₇ independently of each other arehydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen orsulfur; C₂-C₂₄alkenyl, phenyl, C₇-C₉phenylalkyl or —OR₅, R₈, R₉ and R₁₀independently of each other are hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl whichis interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, phenyl orC₇-C₉phenylalkyl, and n is 1, 2, 3, 4, 5, 6, 7 or
 8. 2. A functionalizednanoparticle according to claim 1 comprising on the surface additionallya covalently bound radical of the formula II

wherein the nanoparticle is a SiO₂, Al₂O₃ or mixed SiO₂ and Al₂O₃nanoparticle, R₁₁ is C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

amino-, mercapto- or hydroxyl substituted C₂-C₂₄alkyl; amino-, mercapto-or hydroxyl substituted C₂-C₂₄alkyl which is interrupted by oxygen,sulfur or

C₂-C₂₄alkenyl, C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkenyl, a polymerizablegroup or a polymer, R₁₂ and R₁₃ independently of each other arehydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen orsulfur; C₂-C₂₄alkenyl, phenyl, C₇-C₉phenylalkyl, —OR₁₅,

R₁₄ is hydrogen, C₁-C₂₅alkyl or C₃-C₂₅alkyl which is interrupted byoxygen or sulfur; R₁₅ is hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which isinterrupted by oxygen or sulfur; C₂-C₂₄alkenyl, phenyl,C₇-C₉phenylalkyl,

or the nanoparticle surface, R₁₆ and R₁₇ independently of each other arehydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkyl which is interrupted by oxygen orsulfur; C₂-C₂₄alkenyl, phenyl, C₇-C₉phenylalkyl or —OR₁₅, R₁₈, R₁₉ andR₂₀ independently of each other are hydrogen, C₁-C₂₅alkyl, C₃-C₂₅alkylwhich is interrupted by oxygen or sulfur; C₂-C₂₄alkenyl, phenyl orC₇-C₉phenylalkyl.
 3. A functionalized nanoparticle according to claim 1,wherein R₁ is an additive selected from the group consisting of phenolicantioxidants, benzofuran-2-ones, sterically hindered amines, aminicantioxidants, 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, phosphites,phosphonites, thioethers, benzophenones, α-activated acetophenones,bisacylphosphinoxides (BAPO), mono-acylphosphinoxides (MAPO),alkoxamines, thioxanthones, benzoins, benzil ketals, benzoin ethers,α-hydroxy-alkylphenones and α-aminoalkylphenones.
 4. A functionalizednanoparticle according to claim 1, wherein R₁ is

R₂₄ is C₁-C₂₅alkyl, hydroxyl-substituted C₂-C₂₄alkyl;hydroxyl-substituted C₂-C₂₄alkyl which is interrupted by oxygen, sulfuror

C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₂₅ is C₁-C₂₅alkyl or C₂-C₂₅alkenyl, R₂₆ is hydrogen or methyl, R₂₇ ishydrogen or methyl, R₂₈ is hydrogen or

R₂₉ is C₁-C₄alkylene, R₃₀ and R₃, are each independently of the otherhydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl or C₅-C₈cycloalkyl, R₃₂and R₃₃ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₇-C₉phenylalkyl, phenyl or C₅-C₈cycloalkyl, R₃₄ and R₃₅ are eachindependently of the other hydrogen, halogen, C₁-C₄alkyl, —CN,trifluoromethyl or C₁-C₄alkoxy, R₃₆ is a direct bond or —O—, R₃₇ ishydrogen, —O^(), C₁-C₂₅alkyl, C₂-C₂₀alkenyl, C₂-C₂₀alkinyl,C₁-C₂₀alkoxy, C₅-C₁₂cycloalkoxy, C₇-C₂₅aralkoxy, C₆-C₁₂aryloxy,C₇-C₉phenylalkyl, C₅-C₁₂cycloalkyl, phenyl, naphthyl, hydroxyethyl,C₂-C₂₅alkanoyl, benzoyl, naphthoyl or C₂-C₂₀alkoxyalkanoyl, R₃₈ ishydrogen or an organic radical, R₃₉ and R₄₀ are each independently ofthe other hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl or phenyl, R₄₁ ishydrogen, halogen or C₁-C₁₈alkyl, R₄₂ is hydrogen, C₁-C₁₈alkyl orC₇-C₉phenylalkyl, R₄₃ and R₄₄ are each independently of the otherhydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, di(C₁-C₄alkyl)amino, hydroxyl or

is hydrogen, C₁-C₁₈alkyl, C₁-C₁₈alkoxy or

R₄₆ and R₄₇ are each independently of the other hydrogen, hydroxyl,C₁-C₁₈alkyl, phenyl, C₁-C₁₈alkoxy or C₇-C₉phenylakyl, R₄₈ is a directbond or oxygen, R₄₉ and R₅₀ are each independently of the otherC₁-C₁₈alkyl, C₇-C₉phenylalkyl, cyclohexyl, phenyl, or phenyl substitutedby 1 to 3 alkyl radicals having in total 1 to 18 carbon atoms, R₅₁, R₅₂and R₅₃ are each independently of the others hydrogen, halogenC₁-C₄alkyl or C₁-C₄alkoxy, R₅₄ is C₁-C₂₀alkyl, C₅-C₈cycloalkyl,C₇-C₉phenylalkyl or phenyl, R₅₅ is C₁-C₂₅alkyl, R₅₆ is methylene orethylene, R₅₇ is methylene or ethylene, R₆₂ is hydrogen or C₁-C₁₈alkyl,R₆₃ and R₆₄ are each independently of the other hydrogen, C₁-C₁₈alkyl,C₁-C₁₈alkoxy, C₁-C₄alkylthio, morpholinyl, C₇-C₉phenylalkyl of phenyl,R₆₅ and R₆₆ are each independently of the other C₁-C₁₈alkyl, R₆₇ isC₂-C₄alkylene, R₆₈ is hydrogen or C₁-C₁₈alkyl, R₆₉ is C₃-C₇alkylene, R₇₀and R₇₁ are each independently of the other C₁-C₈alkyl orC₇-C₉phenylalkyl, R₇₂ and R₇₃ are each independently of the otherC₁-C₈alkyl or R₇₂ and R₇₃ are together —CH₂CH₂—O—CH₂CH₂— thus formingwith the nitrogen atom to which they are attached a morpholinyl ring,R₇₄ is hydrogen, C₁-C₁₈alkyl or C₇-C₉phenylalkyl, and x is 1, 2 or
 3. 5.A functionalized nanoparticle according to claim 1, wherein n is
 3. 6. Afunctionalized nanoparticle according to claim 1, wherein R₄ is hydrogenor C₁-C₄alkyl.
 7. A functionalized nanoparticle according to claim 2,wherein R₁₁ is C₁-C₁₈alkyl, C₃-C₁₈alkyl which is interrupted by oxygenor sulfur; or 3-aminopropyl.
 8. A functionalized nanoparticle accordingto claim 1, wherein the functionalized nanoparticle has a sphericalshape.
 9. A functionalized nanoparticle according to claim 1, whereinthe functionalized nanoparticle has a particle size of 10 to 1000 nm.10. A functionalized nanoparticle according to claim 1, wherein thefunctionalized nanoparticle is a silica nanoparticle.
 11. A compositioncomprising a) an organic material subject to oxidative, thermal orlight-induced degradation, and b) at least a functionalized nanoparticleaccording to claim
 1. 12. A composition according to claim 11, whereinthe composition is a coating composition and component (a) is an organicfilm-forming binder.
 13. A composition according to claim 11, whereincomponent (a) is a synthetic polymer.
 14. A composition according toclaim 11, wherein component (b) is present in an amount from 0.01 to80%, based on the weight of component (a).
 15. A composition accordingto claim 11, wherein additional additives are present besides thecomponents (a) and (b).
 16. A process for stabilizing, flame-retardingand/or compatibilizing an organic material which is subject tooxidative, thermal or light-induced degradation, which comprisesincorporating therein, or applying thereto, at least one functionalizednanoparticle according to claim
 1. 17. A process for photoinitiatingin-situ polymerization or hardening of a pre-polymeric nanocomposite orsol to a nanocomposite material, which comprises incorporating therein,or applying thereto, at least one functionalized nanoparticle accordingto claim
 1. 18-19. (canceled)
 20. A process for preparing a reinforcedcoating with improved scratch resistance on a surface, which comprisestreating the surface with a coating composition comprising afunctionalized nanoparticle according to claim 1 and then drying and/orcuring the coating composition.
 21. A functionalized nanoparticleaccording to claim 1, wherein the functionalized nanoparticle has aparticle size of 10 to 500 nm.